Article

Mineralogy and Geochemistry of Mud Volcanic

Ejecta: A New Look at Old Issues (A Case Study from
the Bulganak Field, Northern Black Sea)
Ella Sokol 1, Svetlana Kokh 1,*, Olga Kozmenko 1, Sofya Novikova 1, Pavel Khvorov 2,
Elena Nigmatulina 1, Elena Belogub 2 and Maxim Kirillov 1
1 VS Sobolev Institute of Geology and Mineralogy Siberian Branch Russian Academy of Sciences,
3 Koptyug Avenue, 630090 Novosibirsk, Russia; sokol@igm.nsc.ru or sokol_ag@mail.ru (E.S.);
olg@igm.nsc.ru or okozmenko@gmail.com (O.K.); sa_novikova@inbox.ru (S.N.); helena@igm.nsc.ru (E.N.);
kirillovm@igm.nsc.ru (M.K.)
2 Institute of Mineralogy of the Urals Branch of the Russian Academy of Sciences, 456317 Miass, Russia;

khvorov@mineralogy.ru (P.K.); belogub@mineralogy.ru (E.B.)

* Correspondence: s.n.kokh@gmail.com or zateeva@igm.nsc.ru; Tel.: +7-383-333-21-49

Received: 16 July 2018; Accepted: 6 August 2018; Published: 8 August 2018

Abstract: We characterise the mineralogy and geochemistry of Oligo-Miocene Maykopian shales

that are currently extruded by onshore mud volcanoes of the Kerch-Taman Province (the Northern
Black Sea) from the depths of ~2.5–3 km. The ejected muds are remarkable by highly diverse
authigenic mineralogy that comprises glauconite, apatite, siderite, mixed Fe–Mg–Mn–(Ca) and
Mn–Ca–Fe-carbonates, pyrite, marcasite, sphalerite, cinnabar, chalcopyrite, nukundamite, akantite,
native Cu, Au and Au–Ag alloys. Precise geochemical techniques and high-resolution methods are
applied to study the composition of bulk rocks, sulphide and carbonate fractions, as well as
individual mineral species, including trace element and isotopic compositions of carbonates (C, O)
and pyrite (S). Mineralogy of clastic and heavy fractions is used as a provenance tracer.
Oxygen-deficient to weakly sulphuric deposition conditions are inferred for the parent sediments
proceeding from trace element partitioning between carbonate, sulphide, and metallic phases. The
main conclusion of the study is that onshore mud volcanoes of the region only transport buried
sedimentary material and authigenic minerals they store to the ground surface.

Keywords: authigenic minerals; mud volcano; Maykop shale; Kerch-Taman Province; carbonate;
sulphide; trace element partitioning; suboxic deposition conditions

1. Introduction
Mud volcanoes (MVs), which are actually “tectonic windows” into the deeper subsurface, have
attracted the attention of geoscientists for at least 150 years [1–6]. The previous studies mainly
address the morphology of volcanic edifices; the mechanisms, duration and periodicity of eruptions;
the relations of mud volcanism with geological settings, overpressure zones, and oil and gas
reservoirs; the geochemistry of MV fluids and mud (to a lesser extent), with implications for the
compositions and depths of mobilised sediments; and the role of mud volcanism in the degassing of
deeply buried sediments [2,7–17].
Meanwhile, the mineral-forming potential of mud volcanism has been less studied. Two most
obvious types of mineral-forming processes are (1) surface and near-subsurface precipitation of salts
(chlorides, borates, sulphates, and carbonates) from aqueous MV fluids on an evaporation barrier
[3,18] and (2) ultra-high temperature alteration (combustion metamorphism) of mud masses
triggered by MV flame eruptions and methane ignition [1,17,19–24]. In both cases, minerals owe

Minerals 2018, 8, 344; doi:10.3390/min8080344 www.mdpi.com/journal/minerals

Minerals 2018, 8, 344 2 of 40

their origin mainly to fluids released through MV edifices. Crystal growth under these conditions
commonly occurs as a disequilibrium process at abruptly changing pressure and temperature,
which leaves imprint on the habits, compositions, and zonation of the solids.
For decades, the mineralogical study of ejected mud masses (MMs) has been mostly focused on
applied issues related to petroleum exploration: identifying layered silicates as proxies of parent
rock maturation degree and mobilisation depth [1,25–27] and heavy minerals as tracers of sediment
provenance and diagenesis [26,28,29]. Detailed investigations into ongoing mineral-forming
processes at offshore MVs and related methane seeps began in the 2000s and have shown that
precipitation of minerals (mainly Ca-bearing carbonates) in mud may be mainly driven by methane
emission and subsequent anaerobic oxidation [30–34]. According to the available knowledge, fluids
appear to be the main mineral-forming agents in mud volcanic events.
We study mud masses (MMs) of ordinary onshore MVs of the Northern Black Sea region (the
Bulganak field of the Kerch-Taman MV Province). This work, aiming at understanding the origin of
diverse authigenic minerals stored in MMs, is a first step toward exhaustive characterisation of the
onshore MV ejecta mineralogy. We have analysed more than twenty mineral species using the
conventional tools and protocols of mineralogical research, and also checked numerous geochemical
criteria discriminating between the mineral assemblages that formed syngenetically with the host
mudrocks and later during mud volcanism.
The Bulganak mud volcanoes are the largest representative active onshore MVs of the region.
They expulse aqueous fluids of a Cl-HCO3/Na type with low (SO4)2− contents and negligible amounts
of H2S [3,18,35]. Having the deepest roots in the area (at least 2.5–3.5 km), these volcanoes bring to
the surface material of a single type: homogeneous marine mudrocks of the Maykop Formation
[3,18]. The Maykop monotonic Oligo-Miocene marine sequence has been quite well documented
being a main source of MVs over the vast area from the Kerch Peninsula in the northern Black Sea
region to the Cheleken Peninsula in the eastern Caspian coast [3,5,8,16,36–39].
We study mineralogy and geochemical signatures of bulk sediments and selected mineral
fractions, as well as individual minerals (siderite, mixed Fe–Ca–Mg- and Mn–Ca–Fe-carbonates,
pyrite, marcasite, sphalerite, cinnabar, Cu and Ag sulphides, metallic species and sulphates) and
mineral generations (early framboidal and late euhedral pyrite), in order to track general patterns of
trace element (TE) partitioning between coexisting minerals. The results are further used to
reconstruct the origin of authigenic mineral assemblages, which potentially may (1) form by
precipitation from (or interaction with) MV fluids or (2) be inherited from the parent Oligo-Miocene
Maykop mudrocks, or (3) have a randomly combined (1) and (2) origin. There is a convincing proof
that authigenic minerals store a detailed record of depositional environments and provide actual
evidence of mineral formation conditions in diverse deposition settings [40–48]. Therefore,
concordant changes in trace element and isotopic signatures of authigenic minerals coexisting in
mud masses can provide a reliable check of their syngenetic origin.

2. Geological Context

2.1. Geological Setting and Paleoenvironments

The Black Sea basin is thought to be oceanic remnants now caught up in continental collision
zones [49]. The Kerch and Taman Peninsulas separated by the narrow Kerch Strait lie in a
geodynamically unstable area, at the junction of three regional-scale tectonic structures: the
Highland Crimea and Greater Caucasus, the Indol-Kuban Trough, and the Kerch-Taman [3,50]. The
Indol-Kuban Trough is a large sedimentary basin extending over 500 km from the Caucasus foothills
in the east, through the Taman Peninsula, as far as the Kerch Peninsula in the west (Figure 1a). The
sea basin currently undergoes enhanced lateral tectonic shortening, with mud volcanoes known at
the front and in the centre of the accretionary wedge [2] (Figure 1a). Efficient dewatering during
diagenetic dehydration reactions (smectite-to-illite conversion), organic matter maturation, and
coupled oil and gas production in the frontal and upper parts of the deforming wedge maintained
Minerals 2018, 8, 344 3 of 40

generation of fluids and thus created undercompaction of sediments, overpressure and buoyancy as
prerequisites for mud volcanism [2].
The Kerch-Taman MV Province is located on the southern periphery of the Indol-Kuban
Trough where it is associated with thick Paleocene–Quaternary sediments that reach a total
thickness of 11 km, including 2500–4000 m of Oligocene–Early Miocene (29–19 Ma) homogeneous
clayey marine sediments known as the Maykop Formation or Maykop Shale. They are source and
parent rocks to the MVs of the vast region and, at the same time, reservoir rocks that store significant
resources of oil and gas in the Taman Peninsula and in the basins bordering the Greater Caucasus
[3,5,36,37,51–55].
The Maykop Formation was deposited in the time of dramatic palaeogeographic changes in the
eastern part of the former Tethys ocean induced by the African/Arabian-Eurasian continental
collision since the Eocene [51]. The collision led to uplift of the Alpine chain and to break-up of the
Tethyan Realm into the southern (circum-Mediterranean) and northern (Paratethyan) domains.
From the Oligocene onward, the northern domain became subject to recurrent isolation from the
Mediterranean [54,55]. The postcollisional isolation of the inland Paratethyan basin, along with a
moderately warm and humid climate, resulted in an estuarine water circulation pattern and
halocline formation, which caused recurrent stagnancy in the water column. Those events were
accompanied by sealevel rise and transgression onto a vast area of the southern Russian Platform.
Thus, the Russian landmass in the north and the Lesser Caucasus–Elburz–Kopet–Dag ranges in the
south were main sources of clastic inputs into that part of the Eastern Paratethys basin. Clastics were
transported to the western Indol-Kuban Trough mainly from the Ukrainian and Donets provenance
areas and were deposited as the Maykop suboxic shales without age-diagnostic fossils
[3,50,52,54,55]. In the Middle Miocene, the southern side of the Indol-Kuban Trough underwent
folding and thrusting, with clay diapirism and mud volcanism at the front. Mud volcanism in the
Kerch-Taman Province culminated in the Middle–Late Miocene but is currently declining [3].
Altogether there are nineteen and fifteen MV fields associated with Maykop Shales in the Kerch and
Taman Peninsulas, respectively. All active MV domes are located in the axial onshore part of the
overpressure zone. Offshore mud volcanism occurs in the southern Sea of Azov and in the northern
continental slope of the Black Sea [3,56–58].
Minerals 2018, 8, 344 4 of 40

Figure 1. (a) Sketch map of the northeastern Black Sea region. Modified after [2]; (b) Location map of
sampled mud volcanoes in the Kerch-Taman MV province. Modified after [3]. Grey colour–onshore
area; white colour–offshore area. Mud volcanoes: Vladislavovsky (1), Nasyr (2), Korolevsky (3),
Tobichek (4), Suyurtash (5), Burash (6), Big Tarkhan (7), Bulganak field (8), Eny–Kale (9),
Soldatsko–Slobodsky (10); (c) Detailed geological map showing locations of mud volcanoes,
geological structures and their sedimentary stratigraphy in the northeastern Kerch Peninsula.
Modified after [59]. 1—Lower Quaternary sand, clay silt, and clay (Q1); 2—Middle Pliocene sand,
clay, and iron ore (Kuyalnik stage N22kl); 3—Lower Pliocene (Pontic stage N2p) shelly limestone, and
clay; 4—Upper Miocene shelly limestone, reefal limestone with bryozoa, and clay (Meotic stage
N1m); 5—Upper Miocene clay, marl, and limestone (Sarmat stage, upper substage N13s3); 6—Upper
Miocene clay, marl, limestone, and sand (Sarmat stage, middle substage N 13s2); 7—Upper Miocene
clay with sand, marl, and shelly limestone interbeds (Sarmat stage, lower and middle substage
N13s1–2); 8—Middle Miocene organic limestone, gypsum, and clay with marl and sand interbeds
(Konk stage N12kn); 9—Middle Miocene organic limestone, gypsum, and clay with marl and sand
interbeds (Karagan stage N12kr); 10—Middle Miocene organic limestone, gypsum, and clay with
marl and sand interbeds (Chokrak stage N12с); limestone aquifers; 11—Oligocene and Lower
Miocene shale and silt (Maykop Formation P3 + N11mk); 12—faults, 13—rivers, 14—stratigraphic
boundaries; 15—mud volcanic field; 16—oceanic crust; 17—Alpine orogens; 18—Post-Eocene thrust;
19—a–large MV domes, b–small MV edifices.

2.2. The Kerch Peninsula: Local Geology and Maykopian Facies

The study area is located in the northwestern Kerch Peninsula, on the southern side of the
Indol-Kuban Trough (Figure 1) [51,53,59]. The present tectonic framework of the area comprises
numerous small W–E folds with curved axes (Figure 1b). There are four W–E anticlinal zones
composed mainly of Neogene sediments [3,50]. Folding in the Kerch Peninsula was often
accompanied by clay diapirism and extrusion of plastic mud by active and fossil mud volcanoes
clustering in cores of large anticlines. The Kerch mud volcanoes are currently undergoing a
gryphon–salsa activity phase, with moderate gas emanation and expulsion of mud and saline
waters. Their features have been exhaustively covered by previous workers [3,18,59–61] and will be
left beyond this consideration.
The Lower and Middle Maykop sediments are ubiquitous in the Kerch Peninsula but are rarely
exposed, being most often buried under mudrocks and recent alluvial and aeolian deposits. The
Middle Maykop section, varying in thickness from hundreds of meters in the southern part of the
peninsula to 1000–2500 m in the north, comprises a clay unit below and a sand-clay unit above. In
the east and northeast, it consists of mostly homogeneous deep-sea mudrocks depleted in both
carbonates and organic matter [62]. The total thickness of the Maykop Formation within this area
approaches its regional maximum of 3700–4200 m. Drilling in the Bulganak MV field revealed
Middle Maykop sediments at a depth of 2000 m and more [3]. The Upper Maykop rocks are
widespread in the Southwestern Plain of the Kerch Peninsula and locally fill synclines in its
north–east [3]. Thin layers of the Maykop Formation crop out locally in cliffs on the southern Azov
Sea coast. The outcrop nearest to the Bulganak MV field is that of the Upper Maykop unit, with
typical siderite lenses and layers, at the Tarkhan Cape (10 km away), while the nearest bedrock
exposure of monotonous mudrocks that belong to this unit is as far as in the Taman Peninsula
(Kamennyi Cape, 50 km away). Both outcrops expose only thin intervals (15 and 5–7 m,
respectively), which we sampled and studied together with the currently extruded mud musses.

2.3. Study Area

The northernmost zone of anticlinal folds (Chegene-Yenikale) lies in the extreme northeast of
the Kerch Peninsula, near the Azov coast, where the largest Bulganak field of mud volcanoes
(Figures 1b and 2) is located in the depression of the same name, 8 km north of Kerch city. The field
occurs on the eroded crest of the Bulganak anticline which has Middle Maykop shales in its core [3].
Several bowl-shaped depressions in the anticline crest are surrounded by nine flat mud volcanic
Minerals 2018, 8, 344 5 of 40

edifices, gryphons, salsas, and mud lakes (Figures 2 and 3). We chose to sample MMs from three
representative mud volcanoes (Andrusov, Trubetskoy, and Tischenko Hills) in the Bulganak field
for detailed mineralogical analyses (Figures 2 and 3).
The Bulganak mud volcanoes extrude solid material from deep parts of the Middle Maykop
section, as it was reconstructed proceeding from the geological setting, drilling data, composition of
mud masses [3], micro-palaeontological data [24], and estimates of fluid generation temperatures
[18,59]. Earlier results show that waters released by different Kerch MVs are similar to pore waters in
the Middle Maykop strata [3,18,24,35,61,63,64]. The MV waters have рН = 7.0–8.7, normally contain
10 to 18 g/L total dissolved solids (TDS) (up to 69.0 g/L), and belong to Cl-HCO3/Na or more rarely to
HCO3-Cl/Na types with low Ca, Mg concentrations and (SO4)2− contents from 0 to 110 mg/L.
Compared with seawater (SW), they exhibit profound freshening for Na, K, Rb, Ca, Mg, Sr, (SO 4)2−,
Cl, and Br (MV water/SW ratios 0.01–0.7), but strong enrichment in mobile B, Li, Ba, P, and As. The
highest trace element concentrations were measured in the Bulganak gryphon and salsa waters
(B—305–1635 ppm; Li—1.5–8.2 ppm) [18]. Abundant current precipitates growing from the MV
waters of the area are chiefly Na–Ca and Na borates (ulexite NaCa(B5O6(OH)6)·5H2O; probertite
NaCa(B5O7(OH)4)·3H2O; borax Na2(B4O5(OH)4)·8(H2O); tincalconite Na6(B12O15(OH)12)·8H2O) with
lesser amounts of Na-bearing carbonates (gaylussite Na2Ca(CO3)2·5H2O and northupite
Na3Mg(CO3)2Cl), and sporadic CaCO3 [18], unlike the calcite-dominated active and dormant
travertine springs from the adjacent Big Tarkhan locality [59].
The generation temperatures of aqueous fluids released from the Bulganak MVs, estimated
using the chemical Mg/Li geothermometer (ТMg/Li) [65], fall within the ТMg/Li range from 76 to 117 °С
(n = 14). The respective depths (НMg/Li) of mud volcanic roots, as inferred from these temperatures
and measured local geothermal gradients (30–35 °C/km) [66,67], vary from 2.5 to 3.5 km. The ТMg/Li
range for the Big Tarkhan travertine springs is 68–78 °C, which corresponds to a depth of 2.0–2.5 km
[59]. Compared with the Big Tarkhan and Taman MVs [64,68], those from the Bulganak field expulse
fluids from greater depths.

Figure 2. Study area. Panoramic view of the Bulganak field of mud volcanism. Google Earth image,
2007.
Minerals 2018, 8, 344 6 of 40

Figure 3. Field view of the Bulganak MV field (September 2017). (a) Main eruptive center of
Andrusov Hill extruding plastic mud masses. (b,c) A bubbling satellite gryphon on the flank of the
main cone (Andrusov Hill). (d) Panoramic view of Tischenko Hill expulsing liquid mud. (e) Bubbling
craters at the top of Tischenko Hill.

3. Materials and Methods

3.1. Sampling
In the course of 2008–2017 field trips, we collected bulk samples of Upper and Middle Maykop
shales from the coastal cliffs, along with fifty samples of liquefied Middle Maykop shales as
currently extruded fresh and slightly weathered mud masses (MMs) from ten mud volcanoes in the
Kerch Peninsula. Eleven large (120 kg) bulk MM samples were taken from edifices in the Bulganak
field for most detailed mineralogical analyses. In the first step, clay and heavy minerals (HM) and
carbonate fractions (≤1 mm) were extracted from the bulk samples and subjected to several
procedures of gravity and electromagnetic separation. They were layered silicates (<2 µm) (1),
concentrates of sulphides (2), Fe-rich carbonates (3), a fraction of Fe-(oxy)hydroxides (4), stable HM
from the clastic fraction (5), light fraction (6) with predominant quartz sand particles and sporadic
fossil remnants consisting mainly of CaCO3. Then pyrite (framboids and euhedral crystals
separately), marcasite and carbonate fractions were hand-picked under a binocular microscope.
Only optically clean grains without visible impurities were selected for the chemical and isotope
analyses.
Minerals 2018, 8, 344 7 of 40

3.2. Analytical Procedures

Most of the analytical procedures were carried out at the Analytical Center for multi-elemental
and isotope research (VS Sobolev Institute of Geology and Mineralogy, Novosibirsk, Russia).
Sulphur isotopic compositions of pyrite and X-ray analyses of bulk sediments were carried out at the
Institute of Mineralogy (Miass, Russia). Laser ablation-inductively coupled plasma-mass
spectrometry (LA-ICPMS) of FeS2 was performed at the Centre for Ore Deposit and Exploration
Science (CODES), University of Tasmania.
The elemental compositions of the Maykop Shale bulk samples and isolated mineral fractions
were studied by the solution analysis using inductively coupled plasma atomic emission
spectroscopy (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS). The
preconditioning procedures included fusion of powdered whole rock samples with lithium borate
following Shatsky et al. [69]; purifying sulphide fractions by 2 wt % HCl with subsequent rinsing in
MQ-water; and digestion of carbonate and purified sulphide fractions in fresh aqua regia. Thus,
obtained solutions were divided into two aliquots for analyses of major and trace elements. The
aliquots for trace element analysis were diluted with 2 wt % HNO3. Major elements (Si, Ti, Al, Fe,
Mg, Ca, Na, K, P, S) were analysed on a IRIS Advantage atomic emission spectrometer (ThermoJarrell
Intertechs Corporation, Atkinson, WI, USA). Scandium was added as an internal standard to correct
matrix effects and instrument drift. The concentrations of trace elements (V, Cr, Mn, Co, Ni, Cu, Zn,
Ga, As, Rb, Sr, Zr, Nb, Mo, Ag, Cd, Sb, Te, Cs, Ba, Hf, Au, Ta, Tl, Pb, Bi, Th, U, and REE + Y) were
determined on an ELEMENT ICP-MS (Finnigan, Waltham, MA, USA), using indium as an internal
standard for correction of matrix effects and instrument drift. The detection limits for trace elements
were in the range 0.01–0.2 µg/L. Precision and accuracy for all elements were estimated to be 5–10 rel
%. Two standards (BCR-2, BHVO-2) were used for monitoring analytical reproducibility.
Hg contents in the bulk samples of sediment and in pyrite and marcasite concentrates were
measured by flameless AAS on a Hg analyser RA-915M (Lumex, Saint-Petersburg, Russia) with a
RP91C pyrolysis attachment. The technical specifications of the instruments allow avoiding special
preconditioning of solid samples. The standard SDPS-3 was used to calibrate the spectrometer.
Relative analytical errors were less than 20% (p = 0.95) for concentrations from 5 × 10−7 to 2.5 × 10−2 wt
% [70].
Scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS) were
applied to several tens of mineral grains and aggregates to determine features of their textures,
morphology, and mineral chemistry. The analyses were performed on a JSM-6380LA scanning
electron microscope (JEOL Ltd., Tokyo, Japan) at an accelerating voltage of 10 kV and a beam
current of 2.0 nA. The chemical compositions of carbonate and sulphide grains were determined by
wavelength-dispersive electron microprobe analysis (EMPA) in carbon-coated polished samples,
using a JXA 8100 electron microprobe (JEOL Ltd., Tokyo, Japan). EMPA analyses of carbonates were
performed using an accelerating voltage of 20 keV, a beam current of 15 nA, a 10 s peak counting
time, and a 3–5 µm beam diameter. The compositions of carbonates were estimated with reference to
natural and synthetic standards: albite (Na), diopside (Mg, Ca), BaSO 4 (Ba), pyrope (Fe), Sr–Si glass
(Sr), Mn-almandine (Mn), ZnFe2O4 (Zn) [71]. The concentrations of impurities in sulphides were
estimated under the operating conditions of 20 keV accelerating voltage, 50 nA beam current, 20 s
total counting time, and a focused incident beam. The standards included FeS 2 (S, Fe), FeAsS (As),
PbTe (Pb), FeNiCo (Co, Ni), Sb-metal (Sb), Mn-almandine (Mn), ZnS (Zn), CuFeS 2 (Cu), CdS (Cd)
and HgS (Hg). The detection limits for the elements were (in wt %): 0.01 for Fe, Mn, As, Cu, and Ni;
0.02 for S and Co; 0.03 for Zn; 0.04 for Sb; 0.05 for Hg; and 0.07 for Cd. Peak overlaps for CaKβ-PKα
and SiKα-SrLα were automatically compensated by the instrument software; the matrix correction
using the ZAF algorithm [72] was applied to raw data prior to recalculation into major oxides or
elements. The analytical accuracy was better than 2 rel % for >5 wt % elements and about 5 rel % for
≤2 wt % elements.
Trace element abundances in FeS2 were determined by the LA-ICPMS technique at the School of
Earth Sciences, University of Tasmania and Centre for Ore Deposit Research (Hobart, Australia). The
analyses were performed on a quadrupole 7900cs mass spectrometer (Agilent, Santa clara, CA, USA)
Minerals 2018, 8, 344 8 of 40

and a 193-nm wavelength COMPex Pro ArF gas laser (Coherent Inc., Santa Clara, CA, USA) with
resonetics constant geometry design produced by the Laurin ablation cell. Each sample was
analysed in a time-resolved mode using (Table S1) ms integration time, 1 point per mass, and 60 s
total acquisition time, with approximately 20–25 s of data collected on the gas background prior to
ablation. Most analyses used a 30-µm spot diameter with a laser repetition rate of 5Hz and a power
set to ~6.5 mJ/pulse. All analyses were normalised to external standards (STDGL3 and GSD-1G) and
to a reference element (Fe) as an internal standard. Analytical errors for most elements were less
than 5% (Table S1), which is the typical precision of LA-ICPMS systems in the multi-element mode.
X-ray diffraction (XRD) analyses of phases in the MMs, Maykop shale bulk samples and
selected fractions were performed on a XRD-6000 diffractometer (Shimadzu Corporation, Kyoto,
Japan) (CuKα1+2 radiation with graphite monochromator), at 4° to 70° 2θ, at a step of 0.5°. Layered
silicates were extracted following the method of Hubert et al. [73] in a <2 µm fraction obtained by a
sedimentation technique using repeated siphoning. According to the recommendations for exact
identification of layered silicates [74], <2 µm fractions were reanalysed after being saturated in
glycerol for 24 h and heated at 550 °C for 1 h. SIROQUANT V.4 software was used to calculation of
the proportions of minerals.
For measurements of C and O stable isotopes, powdered carbonate fractions were dissolved in
100% phosphoric acid at 50 °C for over 48 h and then analysed on a Gas Bench II instrument coupled
with a MAT 253 mass spectrometer (Thermo Finnigan, Waltham, MA, USA). All isotope values are
quoted per mill (‰) using δ-notation relative to the Vienna-PeeDee Belemnite standard (VPDB),
with a standard deviation of less than 0.1‰ for δ 13C and 0.2‰ for δ18O. Sulphur isotopic
compositions of pyrite (quoted as δ34S per mil relative to the Canyon Diablo Troilite (CDT) standard)
were analysed on a Delta+ Advantage mass-spectrometer (Thermo Finnigan, Waltham, MA, USA)
using NBS-123 and IAEA-S-1 standards, with δ34S values reproduced to no worse than 0.15‰ CDT.

4. Results

4.1. Bulk and Trace Element Chemistry of the MMs

Mud masses consist of the liquefied Middle Maykop shale with a moderate amount of sand
and low organic contents (≤0.5 wt %). All MMs are depleted in K (0.7–0.8) relative to Post-Archean
Australian Shale (PAAS) [75] (Tables 1 and 2; Figure 4), which is due to high percentages (up to
25–30%) of kaolinite among layered silicates (mainly illite and interlayered illite-smectite) (Figure 5).
Variable amounts of authigenic and biogenic carbonates, as well as the presence of chemogenic
celestine and barito-celestine, are responsible for variations in Ca and Sr contents. Unlike weathered
MMs, the fresh samples contain more sulphidic than sulphate sulphur and more Fe 2+ than Fe3+. The
MMs are commonly enriched in Na and B relative to PAAS and Li, Cs, U, Zn, Co, V, As, Se, Sb, Hg,
Cd relative to the average upper crust [76] (Figure 4). Excess sodium is mainly present as high-silica
plagioclase of the sand fraction with minor NaCl, while boron mainly resides in Na–Ca and Na
borates [3,18]. The MM samples enriched in Hg and As contain cinnabar and As framboidal pyrite.
Total rare-earth element (REE) contents in the Maykop Shales and MMs are 0.65 of PAAS
(110–124 ppm against 184 ppm) (Table 2), but the PAAS-normalised REE patterns of the samples are
similar to one another and to those of PAAS, being different only in more depleted light rare-earth
elements (LREE) relative to heavy rare earths (HREE), with (LREE/HREE) SN = 0.70–0.75. Their
depletion in LREE, as well as in Cs, Rb, Pb, Th, U, Zr, Hf, Nb, and Ta records “dilution” with quartz,
and kaolinite.
Minerals 2018, 8, 344 9 of 40

Table 1. Major element composition (in wt %) of representative mud masses from the Bulganak mud
volcano area in comparison with Middle and Upper Maykop shales (Kerch-Taman MV province).
Middle Upper
Rocks Maykop Maykop Fresh Mud Masses Weathered Mud Masses
Shale Shale
Mean Mean
Sample T-1-3 BT-18-1 В-3-4 О-1-2 202-2 S В-3-7 203-1s 203-2 S
(n = 10) (n = 11)
SiO2 53.19 60.04 56.61 60.36 57.31 57.63 1.88 57.30 53.93 58.32 56.69 3.96
TiO2 0.81 1.05 0.78 0.88 0.89 0.85 0.05 0.87 0.82 0.85 0.85 0.04
Al2O3 16.48 18.07 14.19 12.73 12.70 13.87 1.50 15.81 14.82 14.23 14.47 0.99
Fe2O3 7.90 * 5.83 * 1.57 2.06 2.19 2.16 0.52 5.18 3.84 5.32 4.80 0.61
FeO n.a. n.a. 4.38 4.18 4.77 4.45 0.25 2.01 2.83 1.55 1.84 0.70
MnO 0.11 0.04 0.07 0.10 0.10 0.09 0.01 0.08 0.08 0.11 0.09 0.01
MgO 3.38 1.95 2.02 1.77 1.93 1.92 0.10 2.20 1.89 1.93 1.89 0.28
CaO 2.44 0.47 1.82 1.84 2.15 1.81 0.29 1.40 1.41 2.26 1.59 0.53
Na2O 1.32 1.37 3.08 2.73 2.93 2.67 0.51 1.87 3.98 1.97 2.90 1.64
K2O 2.87 2.19 2.16 1.90 1.97 2.09 0.19 2.38 2.25 1.98 2.14 0.21
P2O5 0.11 0.10 0.14 0.14 0.13 0.14 0.01 0.13 0.14 0.17 0.14 0.02
H2O− n.a. n.a. 1.57 1.24 1.43 1.53 0.27 1.86 1.84 1.99 2.16 0.60
LOI 9.98 7.84 7.07 5.68 6.16 6.42 0.62 6.71 7.64 6.17 7.44 1.31
СО2 n.a. n.a. 3.99 3.71 4.82 3.93 0.67 2.17 3.27 2.24 2.45 1.28
F n.a. n.a. 0.06 0.06 0.06 0.06 0.00 0.06 0.06 0.05 0.06 0.01
SО3 0.47 0.14 0.07 n.d. 0.07 0.03 0.04 n.d. 0.93 0.25 0.24 0.40
S n.a. n.a. n.d. 0.27 0.15 0.17 0.12 0.10 0.13 0.12 0.07 0.06
Total 99.05 99.07 99.58 99.65 99.75 99.81 0.32 100.14 99.86 99.52 99.81 0.28
* All iron is calculated as Fe2O3; n = number of analyses; n.a. = not analysed; n.d. = not detected; S =
standard deviation.

Table 2. Trace and rare earth element composition (in ppm) of representative mud masses from the
Bulganak mud volcano area in comparison with Middle and Upper Maykop shales (Kerch-Taman
MV province).
Middle Upper
Rock Maykop Maykop Fresh Mud Masses Weathered Mud Masses
Shale Shale
Mean Mean
Sample Т-1-3 BT-18-1 B-3-4 О-1-2 202-2 S B-3-7 203-1s 203-2 S
(n = 10) (n = 11)
Li n.a. 56.6 103 65.6 69.0 82.5 23.4 82.8 77.5 62.6 68.9 13.7
Be n.a. 2.16 1.85 1.68 1.70 1.75 0.18 1.86 1.91 1.83 1.84 0.06
B n.a. 61.4 746 602 638 837 369 549 993 598 810 278
Sc 18.7 20.7 17.3 17.7 15.5 16.6 2.91 18.9 17.5 17.7 18.2 0.68
V 123 158 111 102 101 107 14.3 123 125 115 116 10.8
Cr 145 125 90.1 85.7 83.1 88.9 13.6 102 104 94.9 95.2 10.8
Mn 920 249 637 723 694 657 43.8 601 621 758 665 70.7
Co 19.4 18.2 20.7 21.5 19.4 20.7 2.54 21.9 20.8 18.8 20.9 1.61
Ni 76.0 45.9 49.0 42.6 43.9 45.7 5.03 50.6 49.0 44.2 47.2 3.10
Cu 41.7 38.1 24.1 23.8 22.2 22.9 2.26 24.6 25.7 24.4 24.9 0.57
Zn 87.0 112 94.8 134 114 116 22.7 131 114 112 123 11.1
Ga n.a. 19.4 14.1 12.9 12.6 13.5 1.88 15.5 15.5 14.4 14.6 1.21
Ge n.a. 1.30 1.20 1.13 0.96 1.03 0.11 1.04 0.93 0.88 0.95 0.07
As n.a. 27.2 22.3 22.5 12.7 20.5 4.84 13.6 15.9 14.6 19.6 9.86
Se n.a. 8.69 3.72 5.54 4.17 4.73 1.37 4.38 5.43 5.89 5.00 0.78
Rb 86.3 95.0 84.7 75.0 76.0 80.8 10.3 91.8 89.4 83.1 84.9 7.30
Sr 182 89.8 177 313 578 294 165 184 150 163 152 30.2
Y 21.1 17.2 11.8 12.6 12.2 12.5 0.77 12.1 12.5 13.8 13.4 1.38
Zr 150 92.7 48.0 65.0 53.6 56.3 6.20 51.7 56.8 59.0 58.3 5.82
Nb 12.3 9.27 7.36 7.10 7.30 7.44 0.34 7.88 7.42 7.61 7.58 0.21
Mo 1.00 0.66 0.75 1.27 0.83 1.04 0.45 0.57 2.97 1.25 1.45 1.06
Cd 0.12 0.25 0.21 0.14 0.18 0.16 0.04 0.17 0.20 0.19 0.19 0.03
Sn n.a. 2.19 1.88 1.84 1.80 1.85 0.20 1.99 2.00 1.97 1.91 0.16
Sb 0.73 2.09 1.50 1.88 1.35 1.74 0.29 2.04 2.07 1.58 2.09 0.46
Cs 4.00 6.89 7.92 5.47 5.27 6.06 1.26 7.14 6.41 5.77 6.05 0.96
Ba 347 281 291 273 375 326 82.5 258 264 268 271 16.6
Hf 4.00 5.90 5.04 11.9 6.53 6.52 2.68 5.52 5.30 6.81 6.03 0.74
Ta 3.05 0.36 0.47 0.37 0.35 0.39 0.07 0.41 0.38 0.52 0.41 0.08
W n.a. 0.99 0.82 1.82 1.50 1.15 0.43 1.36 0.86 0.87 0.99 0.25
Hg 0.06 0.06 0.54 0.42 0.47 0.38 0.15 0.51 0.60 0.48 0.43 0.21
Tl n.a. 0.39 0.29 0.27 0.27 0.29 0.02 0.30 0.30 0.30 0.30 0.01
Pb n.a. 17.6 17.0 15.3 16.0 16.5 0.69 16.2 16.6 16.5 16.8 0.85
Minerals 2018, 8, 344 10 of 40

Bi n.a. 0.27 0.19 0.16 0.17 0.18 0.02 0.21 0.19 0.18 0.20 0.02
Th 10.0 10.2 8.20 10.1 8.22 8.78 1.06 9.60 8.73 9.28 9.15 0.37
U 1.99 4.77 3.56 3.81 3.37 3.49 0.23 3.88 3.05 3.93 3.80 0.53
Br n.a. 11.5 71.0 41.4 38.7 47.7 17.1 7.10 67.8 14.9 25. 28.5
La 32.3 22.7 20. 19.7 19.9 20.1 0.89 20.8 20.2 20.7 20.7 0.36
Ce 64.3 52.2 44.1 42.3 43.7 43.7 2.25 46.1 43.2 44.2 44.7 1.30
Pr 7.26 5.90 5.19 5.28 5.20 5.37 0.31 5.45 5.24 5.51 5.44 0.14
Nd 27.0 20.5 19.9 19.1 19.8 19.7 0.51 21.2 18.8 20.9 20.3 1.09
Sm 5.49 4.43 4.34 3.94 4.02 4.08 0.13 4.39 4.27 3.94 4.20 0.19
Eu 1.14 1.02 0.93 0.75 0.87 0.88 0.07 0.88 0.96 0.95 0.93 0.04
Gd 4.55 3.42 3.42 3.39 3.46 3.48 0.15 3.58 3.34 3.53 3.53 0.15
Tb 0.68 0.56 0.47 0.46 0.49 0.48 0.03 0.51 0.47 0.49 0.50 0.02
Dy 4.07 3.04 2.77 2.49 2.52 2.63 0.12 2.80 2.84 2.82 2.84 0.06
Ho 0.83 0.56 0.51 0.47 0.46 0.49 0.03 0.46 0.43 0.50 0.48 0.05
Er 2.28 1.54 1.15 1.28 1.15 1.34 0.25 1.28 1.29 1.43 1.37 0.10
Tm 0.34 0.25 0.20 0.16 0.17 0.19 0.02 0.17 0.18 0.19 0.19 0.02
Yb 2.30 1.47 1.04 0.94 1.13 1.12 0.16 0.99 1.13 1.26 1.21 0.19
Lu 0.35 0.25 0.18 0.13 0.19 0.19 0.04 0.16 0.14 0.19 0.16 0.02
n = number of analyses; n.a. = not analyzed; n.d. = not detected; S = standard deviation.
Concentration (in ppm): 0.002 < Te ≤ 0.12, Au < 0.001, Ag < 1.

Figure 4. PAAS-normalised [75] major (A) and trace (B) element patterns of mud masses (Bulganak
MV field) and Maykop parent rocks (Tables 1 and 2). * Upper crust-normalised [76] data.
Minerals 2018, 8, 344 11 of 40

Figure 5. Chemical weathering ternary after [75].

4.2. Bulk-Rock Mineralogy

The bulk MMs extruded by the Bulganak MVs consist of ~29–35 wt % quartz, ~7–11 wt %
high-silica plagioclase, and 2–5 wt % potassium feldspar (sand fraction); 18–40 wt % illite and mix
illite-smectite (totally); ~12–17 wt % kaolinite, ~2–4 wt % chlorite, 1–4 wt % Fe-rich carbonate, and ~1
wt % calcite. The principal minerals of the clay fraction (<2 µm) isolated from MMs include illite
(61–73 wt %) and kaolinite (13–29 wt %) with minor amounts (<3–7 wt %) of disordered
illite-smectite phases with ~30% of smectite layers. Disordered illite-smectite is more abundant
(12–20 wt %) in clay fractions from other mud volcanoes in the Kerch Peninsula. Quite large
(hundreds of microns) flake fragments of slightly weathered chlorite and muscovite occur in the
coarse fraction but are undetectable in the diffraction patterns of the clay fraction, and rather belong
to clastics transported from the provenance areas.
The Middle Maykop Shale samples from the Azov coastal outcrop share general similarity with
Bulganak MMs in bulk mineralogy, but their clay fraction stores lower amounts of both illite (54–64
wt %) and kaolinite (5–11 wt %) and higher amounts of disordered illite-smectite (11–15 wt %). They
also may contain up to 2 wt % pyrite and/or 4 wt % biogenic calcite and aragonite; <1 wt % Fe-rich
carbonate restricted to a few layers; and sporadic glauconite pellets. The exposed sediments are cut
by numerous veins of gypsum or jarosite and store partially oxidised opaque minerals. As a
consequence, the heavy fraction contains abundant Fe-(oxy)hydroxides.
The mineralogy of heavy clastic fractions from the MMs and Middle Maykop shales of the area
is generally uniform, with a predominant assemblage of ultrastable minerals which are most
resistant to weathering, dissolution and transport. The HM assemblages of all studied samples
mainly contain fine-grained well-rounded, fragments of rutile, ilmenite, kyanite, sillimanite, garnets
and some andalusite. Well-rounded grains of zircon, titanite, magnetite, tourmaline, monazite,
apatite and Cr-spinel are sporadic. Subangular epidote grains predominate among non-resistant
HM, while amphiboles and pyroxenes are angular and few. The Bulganak mud contains lower
percentages of non-resistant HM than the Middle Maykop shales. All sediments also bear clots of
Fe-(oxy)hydroxides composed of amorphous matter and goethite. Fe-(oxy)hydroxides may also
occur as films over fine-grained quartz-Fe-carbonate (± pyrite) aggregates. The ratio of
FeS2/Fe-(oxy)hydroxides in the heavy fraction from the Middle Maykop shale reduces to 1:2, mainly
because of supergene oxidation and hydration of sulphides, which impedes reliable identification of
authigenic mineralization.
Minerals 2018, 8, 344 12 of 40

Authigenic mineral assemblages are diverse, but all MM samples we studied contain
predominant Fe(Mn)-rich carbonates, abundant pyrite and authigenic quartz, as well as some
marcasite, glauconite, and barite found as separate crystals and complex intergrowths (Table 3,
Figures 6–9). Pyrite is the most abundant authigenic mineral in the Middle Maykop shale, marcasite
crystals are also common, whereas Fe-bearing calcite and oligonite do not exceed 10% of sulphides.
The MM aggregates of Fe and Mn-rich mix carbonates, as well as pyrite, commonly contain minor
clayey matter; rarely siderite is found grown together with glauconite pellets (Figure 9g,h).
Compositionally similar carbonates (siderite, ankerite, oligonite) are frequently intergrown, while
aggregation of different carbonate species is rare (Figure 6). Fine-crystalline siderite often coexists
with Fe-(oxy)hydroxides and more rarely with framboidal pyrite (Figure 9f), while only fine pyrite
particles are present on the faces of larger rhombohedral crystals. Some Fe-carbonates coexist with
gypsum (Figure 9e,f), Fe-(oxy)hydroxides, and with fine clots of authigenic apatite. The aggregates
of authigenic carbonates and pyrite contain silica, either as clots, a sort of cement or, rarely, as
euhedral fine crystals (Figures 6b and 9i). The XRD analysis failed to identify polymorphic SiO2
modifications other than quartz.
Barite forms stellar and fibrous aggregates, or rarely intergrowths or irregular grains coexisting
with pyrite and occasionally with sphalerite. The mineral fills cracks in large pyrite crystals, as well
as the space between pyrite framboids. Barite rarely contains up to 2.18 wt % SrO. Celestine (with
6.30–7.45 wt % BaO) is rare and mostly occurs in rims around barite (Figure 9a–c). Gypsum is very
rare, found as aggregates of anhedral grains (<2 µm in size) that coat fine intergrowths of authigenic
silica, siderite, and pyrite (Figure 9d–f).

Table 3. Authigenic minerals identified in the heavy fraction of the mud masses from Bulganak MV
area (optical microscopy, SEM, XRD and EMPA).

Mud Volcano Hill

Phase
Tischenko Andrusov Trubetskoy
Carbonates
Siderite ((Fe,Mg)CO3) ♦ ♦ ♦
Ankerite (Ca(Fe2+,Mg)(CO3)2) ▲ ▲ ▲
Dolomite (CaMg(CO3)2) ● ● ●
Calcite (CaCO3) ●
Oligonite (Fe,Mn,Mg,Ca)CO3 ●
Kutnohorite (Ca(Mn,Mg,Fe2+)(CO3)2) ●
Mn-calcite ((Ca,Mn)CO3) ●
Ca-rhodochrosite ((Mn,Ca)CO3) ●
Sulphides
Pyrite (FeS2) ♦ ♦ ♦
Marcasite (FeS2) ● ● ▲
Cinnabar (HgS) ●
Sphalerite (ZnS) ▲
Cu5FeS6 ●
Chalcopyrite (CuFeS2) ●
Akantite α-Ag2S ●
Pb-S-bearing phase ●
Native elements and alloys
Copper (Cu0) ●
Gold (Au0) ●
Gold-Silver alloy (AuxAg1−x) ●
Sulphates
Barite (BaSO4) ● ● ●
Celestine (SrSO4) ●
Gypsum (CaSO4·2H2O) ● ●
Oxydes/(oxy)hydroxides
Fe(Mn)-(oxy)hydroxides ▲ ▲ ▲
Quartz (SiO2) ▲ ▲ ▲
Silicates
Glauconite (K,Na)(Fe3+,Fe2+,Al,Mg)2(Si,Al)4O10(OH)2 ● ● ●
♦ = abundant phase (>10 vol %), ▲ = rare phase (1–10 vol %), ● = accessory phase (<1 vol %), not filled cell = absent.
Minerals 2018, 8, 344 13 of 40

Figure 6. Morphology of authigenic carbonates from mud masses (Bulganak area). (a) Large
rhombohedral crystals of siderite with rough faces and distinct growth steps; (b) Intergrowth of
fine-grained siderite and quartz. Siderite forms tiny rhombohedral crystals with flat faces and
well-defined edges and corners. Quartz exists as clots with uneven surface or as cement filling voids
between siderite grains; (c) Foliated rhombohedrons of siderite; (d) Large rhombohedral crystal of
Mg-siderite with intricately sculptured faces laminae and smoothed edges and corners; (e)
Intergrowth of rhombohedral siderite and dolomite; crystals have rough faces with distinct growth
steps; (f) Rhombohedral ankerite crystal with rough growth steps. Ankerite forms intergrowth with
quartz. Back-scattered electron (BSE) images. Ank = ankerite; Dol = dolomite; Mg–Sd = magnesian
siderite; Sd = siderite; Qz = quartz. (a,b) = Tischenko Hill; (c–f) = Trubetskoy Hill.
Minerals 2018, 8, 344 14 of 40

Figure 7. Morphology of primary and recrystallised pyrite framboids from mud masses (Bulganak
area). (a) Botryoidal aggregate of primary spherical framboids and partly recrystallised framboids
that acquire cubo-octahedral habits. Most framboids are ordered (sometimes with shared microcryst
orientation) and filled. Crystallites comprising framboids are mostly cubo-octahedral (b) Botryoidal
aggregate of primary spherical framboids buried in matrix. Most framboids are ordered and filled.
One framboid has trigonal symmetry. Framboid crystallites are octahedral and cubo-octahedral; (c)
Sunflower structures with framboidal core rimmed by radiating outer crystals (on the right) and
partly recrystallised framboids buried in matrix; (d) Recrystallised framboids composing a
pseudomorph after a fossil remnant. Framboids that preserve discrete crystallites separated by holes
in the core and rimmed by massive aggregates of agglomerated crystallites correspond to early
recrystallisation. Completely filled spherules correspond to a more progressive stage of
recrystallisation; (e,f) Intergrowth of primary spherical framboids (on the right) and cubo-octahedral
pyrite crystals formed during recrystallisation of framboids (on the left). Framboids consist of
octahedral and cubo-octahedral crystallites (f); (g,h) Aggregate of octahedral and cubo-octahedral
crystals that formed during final stage of framboids recrystallisation. Crystals compose a
pseudomorph after a fossil remnant and are buried in the matrix (g). BSE images. M = matrix; Py =
pyrite; Qz = quartz. (a,c,d) = Tischenko Hill; (b,g) = Andrusov Hill; (e,f,h) = Trubetskoy Hill.
Minerals 2018, 8, 344 15 of 40

Figure 8. Morphology of large pyrite (a–i) and marcasite (j–l) crystals from mud masses (Bulganak
area). (a) Cubo-octahedral pyrite crystal. Some faces are heavily etched; (b,c) Cubic ({100}) crystals.
Crystal faces are heavily etched (b), have stepped growth layers (c) and are dusted with
microcrystals of later generations (b,c). Some crystals show {111} faces (c); (d–h) Octahedral ({111})
crystals and their aggregates. Some crystal faces are heavily etched (e–g), have screw dislocations
(d,g) and are dusted with microcrystals of later generations (d). Pyrite coexists with coccoliths (e),
clay and quartz (f,g); (i) Rounded aggregate of cubo-octahedral crystals ({100} faces are dominated).
Some octahedral faces are heavily etched; (j,k) Tabular (flattened on (010)) and prismatic crystals of
marcasite coexisting with clay and quartz; (l) Twins of marcasite coexisting with clay and quartz. BSE
images. Coc = coccoliths; Py = pyrite; Qz = quartz. (a,b,i,l) = Tischenko Hill; (c–e,h,j,k) = Trubetskoy
Hill; (f,g) = Andrusov Hill.
Minerals 2018, 8, 344 16 of 40

Figure 9. Morphology of sulphates, glauconite and quartz from mud masses (Bulganak area). (a)
Intergrowth of Sr-barite, celestine and quartz. Celestine forms rims around earlier Sr-barite; (b)
Star-like aggregate of barite; (c) Barite filling space between pyrite crystallites; (d) Prismatic gypsum
crystals coexisting with recrystallised pyrite framboids and quartz; (e,f) Granular aggregates of
unfaceted gypsum grains covering intergrowths of fine-grained siderite and recystallised pyrite;
(g,h) Intergrowth of rhombohedral Mg-siderite and glauconite pellets. Mg-siderite crystals have
rough faces. Glauconite pellets are composed of aggregate of overlapping micaceous flakes with no
preferred orientation; (i) Quartz euhedral crystals. BSE images. Brt = barite; Sr-Brt = Sr-barite; Clt =
celestine; Glt = glauconite; Gp = gypsum; Py = pyrite; Qz = quartz; Sd = siderite. (a,b) = Trubetskoy
Hill; (c,g,h,i) = Andrusov Hill; (d–f) = Tischenko Hill.

4.3. Authigenic Mineralogy and Mineral Chemistry

4.3.1. Carbonates: Morphology, Chemistry, and Isotopes

FeCO3-rich solid solutions and ankerite are the principal authigenic phases in the heavy fraction
of the Bulganak MMs. Mn-rich carbonates are of limited occurrence and dolomite is very rare
(Tables 3 and 4, Figure 10). Most calcite resides in forameniferal tests.
Minerals 2018, 8, 344 17 of 40

Table 4. Representative EMPA analyses of authingenic carbonates from mud masses.

Mineral CaO FeO MgO MnO Na2O SrO ZnO Total FeCO3 MgCO3 CaCO3 MnCO3
wt % mol %
LLD 0.01 0.01 0.03 0.01 0.02 0.02 0.02
Tischenko hill
Sd * 4.43 49.85 3.13 0.33 0.18 bdl bdl 57.95 81 9 9 1
Sd 5.23 44.90 7.50 0.07 0.06 0.06 bdl 57.82 70 20 10 0
Sd 5.97 49.16 2.97 0.43 0.14 0.06 0.12 58.85 79 8 12 1
Sd 7.31 46.99 2.40 0.82 0.08 0.09 0.12 57.81 77 7 15 1
Sd 5.19 39.65 10.47 1.50 0.15 0.06 bdl 57.04 60 28 10 2
Sd 1.19 40.03 11.07 6.51 0.13 bdl 0.05 58.98 59 29 2 10
Olig * 4.41 29.02 8.75 14.42 0.11 0.05 0.19 56.96 44 25 9 22
Olig * 5.80 24.29 6.77 21.28 0.18 bdl 0.15 58.54 37 19 11 33
Olig * 5.15 25.16 7.86 20.70 0.10 0.07 0.14 59.18 38 21 10 31
Kut 22.86 1.96 6.84 25.71 0.22 0.06 bdl 57.70 3 18 42 37
Dol 29.47 5.62 17.28 bdl bdl bdl bdl 52.37 8 42 50 0
Andrusov hill
Sd * 4.61 49.48 1.95 0.39 0.23 bdl 0.10 56.80 83 6 10 1
Sd 6.38 50.15 0.55 0.83 0.23 bdl bdl 58.17 84 2 13 1
Sd 4.26 47.89 4.66 0.93 0.18 0.09 bdl 58.04 77 13 9 1
Sd 1 5.07 45.43 7.40 0.38 bdl 0.08 0.08 58.52 69 20 10 1
Sd 4.89 45.63 7.80 0.39 0.06 bdl 0.12 58.91 69 21 9 1
Ank 33.04 13.33 11.33 0.24 bdl bdl bdl 57.99 18 26 55 1
Ank 31.72 11.22 13.35 0.15 bdl 0.09 bdl 56.56 15 32 53 0
Ank 31.59 11.91 13.21 0.19 bdl 0.25 bdl 57.21 16 30 54 0
Ca-Rhod 2 15.10 1.27 0.75 40.47 0.12 bdl bdl 57.88 2 2 30 66
Trubetskoy hill
Sd * 5.16 48.44 4.35 0.48 0.17 bdl 0.07 58.67 76 12 10 1
Sd 9.75 41.93 2.17 4.37 0.20 bdl 0.06 58.53 66 6 20 7
Sd 1.58 46.23 10.65 0.25 bdl bdl bdl 58.74 68 28 3 0
Ank 31.57 9.47 15.54 0.20 bdl 0.17 bdl 56.97 12 35 52 1
Ank 31.53 12.70 12.27 0.26 0.05 0.41 bdl 57.22 17 29 53 1
Ank 31.66 13.81 11.21 0.17 bdl 0.10 bdl 57.00 19 26 55 0
Mn-Cal 31.64 0.33 0.15 26.04 0.08 0.05 bdl 58.31 1 1 59 39
Cal 3 52.29 1.95 0.40 0.19 bdl 0.08 bdl 54.98 3 1 96 0
Dol 28.85 5.84 17.83 1.10 bdl bdl bdl 53.62 8 42 48 2
LLD = lower limit of detection; bdl = below detection limit. Concentrations of BaO: 1—0.08 wt %;
2—0.12 wt %; 3—0.07 wt %; other samples < 0.03 wt % (LLD). * grain size < 5 µm; other grains are

10–300 µm. Ank = ankerite, Cal = calcite, Ca-Rhod = Ca-rhodochrosite, Dol = dolomite, Kut =
kutnohorite, Mn-Cal = Mn-calcite, Olig = oligonite, Sd = siderite.
Minerals 2018, 8, 344 18 of 40

Figure 10. Triangular diagrams: (a) CaCO3–MgCO3–(FeCO3 + MnCO3) and (b) FeCO3
–MnCO3–(CaCO3 + MgCO3) showing the composition of authigenic carbonates from mud masses
(Bulganak area). Triangles—Andrusov Hill, squares—Trubetskoy Hill, circles—Tischenko Hill; open
symbols—fine-grained carbonates (≤5 µm), filled symbols—large carbonate crystals (>10 µm).
Asterisks are compositions of carbonates synthesized at 25 °C (open symbols) and 70 °C (filled
symbols) [77]. Shadowed field corresponds to siderite-magnesite solid solutions synthesized at 250
°C [78].

Siderite predominantly occurs as intergrowths of tiny rhombohedral crystals (≤5 µm) or less
often as separate and aggregated large rhombohedra (up to 300 µm) (Figure 6). The tiny
rhombohedra have flat faces and well-defined edges and corners (Figure 6a), while the larger
crystals are commonly obtuse rhombohedra (Figure 6a,c–e) with intricately sculptured faces
(tile-like) and often rounded edges and corners; some siderite crystals are hollow case-like or
massive. The morphologically similar siderite crystals in different samples show no systematic
compositional difference. The tiny crystals commonly contain 75–83 mol % FeCO3 and ≤1 mol %
MnCO3; with both CaCO3 and MgCO3 contents of about 10 mol % (Table 4). Larger rhombohedra are
richer in MgCO3 (up to 20–29 mol %); CaCO3 (20 mol %), and MnCO3 (7–10 mol %). All siderites
contain impurities: up to 0.35 wt % Na2O, 0.12 wt % ZnO, and 0.13 wt % SrO.
Minerals 2018, 8, 344 19 of 40

Ankerite (52–55 mol % CaCO3, 26–35 mol % MgCO3, 12–19 mol % FeCO3, and ≤1 mol % MnCO3)
(Table 4) occurs as aggregates of fine grains or larger rhombohedral crystals with complex rough
face surfaces, blunt edges and corners (Figure 6f).
Mn carbonates are coarse crystals of kutnohorite, Mn-calcite and Ca-rhodochrosite and
fine-grained clots of mix carbonates (oligonite), with high contents of FeCO 3 (37–44 mol %), MnCO3
(22–33 mol %), MgCO3 (19–25 mol %) and low CaCO3 (9–12 mol %) (Table 4).
Dolomite (CaMg(CO3)2) forms sporadic quite coarse rhombohedra (with 42–45 mol % MgCO3,
5–8 mol % FeCO3, and <2 mol % MnCO3) (Figure 6e). Few calcite rhombohedra (with <3 mol %
FeCO3, MgCO3, and MnCO3) were found in MMs from Trubetskoy Hill only.
The bulk fractions of Fe(Mn)-rich carbonates host Mn (1.53–1.73 wt %), Zn (237–439 ppm), Sr
(217–278 ppm) and Ba (260–327 ppm). Their PAAS-normalised REE patterns show LREE (La, Ce, Pr,
Nd) depletion relative to HREE (Er, Tm, Yb, Lu) ((LREE/HREE) SN = 0.30–0.49) (Figure 11). This is the
only seawater-like signature of REE distribution typical of authigenic Fe(Mn)-rich carbonates, which
lack other features, such as negative Ce or positive Y/Ho anomalies, and thus can be inferred to have
formed in an oxygen-deficient environment [79,80].
The δ13C and δ18O values were measured in hand-picked siderite and ankerite fractions from
Andrusov and Trubetskoy Hills, and in siderite and oligonite fractions from Tischenko Hill.
Siderites are markedly enriched in 18O, with δ18O from +5.2‰ VPDB (36.2‰ VSMOW) to +5.9‰
VPDB (36.9‰ VSMOW), but ankerite and oligonite have lower δ18O values (+1.0‰ to +1.8‰ VPDB).
The δ13C values in all studied carbonates vary between +2.1‰ and +3.7‰ VPDB. Siderite from
Trubetskoy Hill has the heaviest C isotope composition (+3.5 to +3.7‰ VPDB). All authigenic
carbonates are drastically different from the isotopically heavy travertines of the Big Tarkhan
springs (δ13Cav = +11.8 to +12.5‰ VPDB; δ18Oav = +10.5 to +12.0‰ VPDB) (Table 5).

Figure 11. PAAS-normalised [75] REE patterns of fine-crystalline siderite (1), crystalline siderite (2),
and ankerite (3) fractions from mud masses (Bulganak area).
Minerals 2018, 8, 344 20 of 40

Table 5. Isotope composition of authigenic carbonates and pyrite from mud masses (Bulganak MV
areas) in comparison with Big Tarkhan travertine.

δ 13C δ18O δ18O δ34 S

Location Mineral
(VPDB), ‰ (VPDB), ‰ (VSMOW), ‰ (CDT), ‰
Andrusov hill Ankerite +2.1 ± 0.1 +1.9 ± 0.2 +32.8 ± 0.2
Andrusov hill Ankerite +2.2 ± 0.1 +1.8 ± 0.2 +32.7 ± 0.2
Trubetskoy hill Ankerite +2.2 ± 0.1 +1.0 ± 0.2 +31.9 ± 0.2
Trubetskoy hill Ankerite +2.0 ± 0.1 +1.2 ± 0.2 +32.1 ± 0.2
Tischenko hill Oligonite +2.8 ± 0.1 +1.3 ± 0.2 +32.2 ± 0.2
Andrusov hill Siderite +3.3 ± 0.1 +5.9 ± 0.2 +36.9 ± 0.2
Trubetskoy hill Siderite +3.5 ± 0.1 +5.2 ± 0.2 +36.2 ± 0.2
Trubetskoy hill Siderite +3.7 ± 0.1 +5.5 ± 0.2 +36.5 ± 0.2
Tischenko hill Siderite +3.7 ± 0.1 +5.4 ± 0.2 +36.4 ± 0.2
Big Tarkhan spring Calcite * +8.1 ± 0.1 +11.0 ± 0.2 +42.3 ± 0.2
Big Tarkhan spring Calcite * +10.7 ± 0.1 +12.7 ± 0.2 +44.0 ± 0.2
Big Tarkhan spring Calcite * +11.6 ± 0.1 +12.8 ± 0.2 +44.1 ± 0.2
Big Tarkhan spring Calcite * +12.1 ± 0.1 +12.9 ± 0.2 +44.2 ± 0.2
Andrusov hill Pyrite frambiods +8.94 ± 0.15
Andrusov hill Pyrite crystals +8.23 ± 0.15
Andrusov hill Pyrite crystals +6.23 ± 0.15
Trubetskoy hill Pyrite frambiods ** +7.40 ± 0.15
Trubetskoy hill Pyrite frambiods ** +5.65 ± 0.15
Trubetskoy hill Pyrite crystals +4.02 ± 0.15
Trubetskoy hill Pyrite crystals +4.18 ± 0.15
Tischenko hill Pyrite frambiods ** +0.38 ± 0.15
Tischenko hill Pyrite crystals +0.36 ± 0.15
Tischenko hill Pyrite frambiods -1.53 ± 0.15
* After [59]; ** pseudomorphs after fossil organic remnant.

4.3.2. FeS2: Morphology

Marcasite occurs as intergrowths of tabular (flattened on (010)) and prismatic crystals or twins
25–200 µm in size (Figure 8i,j).
Pyrite has several common modes of occurrence in MMs: (1) botryoidal aggregates of
framboids, sometimes partly recrystallised; (2) pseudomorphs after fossil organic remnants
composed of framboids; (3) coarse (up to 200 µm) euhedral crystals and their intergrowths (Figures 7
and 8). Pyrite is often intergrown with Fe-rich authigenic carbonates and quartz (both sandy and
authigenic), less often with Fe-(oxy)hydroxides, and very rarely with gypsum (Figures 8e and 9d,f),
metallic copper and akantite (Figure 12e,i). The space between crystals and framboids is often filled
with clayey matter, or occasionally with some fine authigenic apatite, barite, and very rare coccolith
(Figure 9c).
Minerals 2018, 8, 344 21 of 40

Figure 12. Morphology of copper sulphides, cinnabar, sphalerite, silver sulphide and native elements
from mud masses (Bulganak area). (a,b) Intergrowth of chalcopyrite and Cu–Fe-sulphide (close to
Cu5FeS6-stoichiometry). Chalcopyrite forms tetrahedrons. Cu5FeS6 occurs as reniform aggregate
consisting of numerous star-like microliths with orthorhombic (?) symmetry (b); (c) Euhedral crystal
of cinnabar with sharp edges and vertices; (d) Sphalerite tetrahedron with sharp edges and vertices;
(e) Thin plate of copper coexisting with pyrite, Fe-(oxy)hydroxides, quartz and detrital albite; (f) EDS
spectrum of copper; (g,h) An irregular particles of Au–Ag alloy decorated by later pancake-like
overgrowths of gold; (i) Aggregate of silver sulphide (Ag2S) coating a pyrite crystal. (a–e,g–i) BSE
images. Ab = albite; Ccp = chalcopyrite; Cin = cinnabar; Cu0 = copper; Sp = sphalerite; Qz = quartz.
(a–c,e,g,h) = Tischenko Hill; (d,i) = Andrusov Hill.

Framboids are mostly spherical with diameters from 5 to 50 µm (10–20 µm on average) and
consist of spherical, cubic, cubic-octahedral, or more rarely octahedral crystallites, with sizes from
0.5 to 3 µm (Figure 7), arranged most often in an ordered way (sometimes with shared orientations)
and rarely with distinct pentagonal or trigonal symmetry (Figure 7b). Some framboids are composed
of randomly aggregated crystals. Most of framboids contain intergrown crystallites (filled), while
some are open and composed of discrete particles. The space between framboids (both primary and
recrystallised) is frequently filled with matrix material (Figure 7b,c).
Minerals 2018, 8, 344 22 of 40

Framboids show all stages of recrystallisation, propagating commonly from rim to core and
ending with the formation of spherules (Figure 7d) which become progressively more euhedral until
they evolve into octahedral and cubic-octahedral crystals (Figure 7e,f). The cores of framboids
preserve crystallites which are separated by holes and/or are rimmed by massive aggregates of
agglomerated particles. Framboids formed at the next stage are completely filled spherules (2–30 µm
in diameter); the final stage produces compact aggregates of 3–10-µm isometric particles or euhedral
crystals (Figure 7d–h). There are also so-called sunflower structures with framboidal cores rimmed
by radiating outer microcrystals (Figure 7c).
Recrystallised pyrite occurs as octahedral, cubic-octahedral or rarely cubic crystals (up to
100–200 µm in size) and their intergrowths (Figure 8). Larger crystals commonly have sculptured
surfaces, heavily etched faces and corners, and are dusted with fine cubic or cubic-octahedral
microcrystals of later generations. The morphological diversity of authigenic pyrite leaves no doubt
about several episodes of nucleation and growth during sedimentation and sediment maturation.
Generally, all studied pyrites have textures indicative of early diagenetic process [81].

4.3.3. FeS2: Main and Trace Element Composition and Isotopy

The concentrations of main and some trace elements were determined by the EMPA method at
the FeS2 grain sites free from inclusions. The S/Fe ratio (1.97–1.98) in the framboid crystallites fits the
FeS2 stoichiometry. They contain up to 0.91 wt % of Mn. The matrix also has the S/Fe ratio ~2 but has
a deficit of totals (1.3–3.0 wt %) and contains up to 2.19 wt % Mn. Pyrite crystals with the S/Fe ratio
about 1.99 host up to 1.33 wt % Mn. EMPA analyses also reveal patchy distribution of Mn, As (up to
0.60 wt %), Cu, Co, and Ni (up to 0.14 wt %, 0.10 wt % and 0.16 wt %, respectively) in pyrite.
Marcasite corresponds to the FeS2 stoichiometry (S/Fe = 1.98–1.99) and contains up to 0.88 wt % Mn
and 0.31 wt % Cu.
Trace element (TE) contents were estimated by ICP-MS in hand-picked concentrates of early
pyrite (framboids and pseudomorphs after fossil remnants) and later crystals. The contents of Hg
were measured by flameless AAS, in separate aliquots (Table 6). The contents of Zn, Cu, V, Ni and
Ag in replica samples may differ by a factor of 1.5–2, possibly, because of the “nugget effect”, which
reveals microinclusions of the respective minerals [81–83]. It is more correct and spectacular to
compare the TE contents in the pyrite concentrates, which all contain clayey inclusions, as
expressed via the relative enrichment factor: EFelement = ([C]element/[C]Al)sample/([C]element/[C]Al)lithogenic [45].
In our case, the TE contents were normalised to those of Ga (EFelement =
[C]element/[C]Ga)sample/([C]element/[C]Ga)PAAS), which is a close geochemical equivalent of Al [84]. The EF
distribution spectra of all pyrite fractions are similar (Figure 13), with three peaks separated by
minimums in Zn and Cd: peak I in Mn, Co, Ni, Cu (flat, EF = 10 2–103); peak II in As, Mo, Hg (sharp,
EF = 103–104); peak III in Sb, Au, Pb (bell-shaped, EF = 102–104). The Cd minimum is prominent in all
fractions, while that of Zn is more diffuse as Zn contents are quite high in the Andrusov Hill
concentrates where sphalerite exists as crystals or possibly as micro-inclusions in pyrite.

Table 6. Trace element contents in pyrite fractions from mud masses, Bulganak MV area,
Kerch-Taman MV province. ICP-MS data, ppm.

Location Andrusov Hill Trubetskoy Hill Tischenko Hill

Pseudomorphs
Euhedral Euhedral Euhedral
Element Framboids after Fossil Framboids Framboids
Crystals Crystals Crystals
Remnants
Ti 27.3 471 2.63 1.22 1.68 3.53 8.20
Mn 4971 2529 585 2173 1465 3144 1605
Co 182 145 18.7 134 32.0 130 71.0
Ni 445 386 46.0 240 63.0 325 120
Cu 797 412 70.0 358 62.0 179 90.0
Zn 965 57.0 197 56.0 25.0 83.0 46.0
As 1148 1001 134 331 175 761 329
Hg 4.20 1.25 7.50 1.30 2.50 1.65 2.40
Minerals 2018, 8, 344 23 of 40

Mo 111 105 17.5 22.1 18.5 70.0 19.4

Cd 0.61 0.5 0.09 0.26 0.17 0.32 0.15
Sb 17.6 43.0 2.32 5.00 2.13 18.2 4.23
Au * 0.08 0.08 0.01 0.06 0.02 0.05 0.02
Pb 402 337 47.0 140 46.0 309 78.0
Ga 0.53 0.10 0.13 0.28 0.19 0.32 0.18
V 7.18 8.08 0.91 2.67 1.65 4.32 2.04
Cr 12.6 9.58 1.85 10.1 3.18 3.47 1.29
* the contents of Au were not determined in the bulk sediment sample.

Figure 13. Trace element enrichment of framboidal pyrite and pyrite pseudomorphs after fossil
remnants versus large euhedral pyrite crystals. ICP-MS data for bulk fractions (Table 6). Relative
enrichment factor EFelement = ([C]element/[C]Ga)sample/([C]element/[C]Ga)PAAS [45]. PAAS after [75]. 1 = pyrite
pseudomorphs after fossil remnants (Andrusov Hill); 2 = large euhedral pyrite crystals (Andrusov
Hill); 3 = large euhedral pyrite crystals (Trubetskoy and Tischenko Hills); 4 = framboidal pyrite
(Andrusov, Trubetskoy and Tischenko Hills).

The EF patterns of framboidal pyrite from different samples are very similar to one another and
are generally the same, though at a lower level of values, for the later-generation crystals. The
highest EF values correspond to the concentrate of framboids after fossil remnants. Note also that
this is the only pyrite fraction with order V enrichment. The abnormal EF Hg values for the
concentrate of pyrite crystals from Andrusov Hill may be due to the presence of cinnabar
microinclusions. The difference in TE compositions of early and later pyrite generations is minor for
As, Mo, Sb but is much greater for Co, Ni, Cu, Au, and Pb (Figure 13).
TE contents in pyrite and marcasite were determined by LA-ICPMS (Tables 7 and 8), which
confirmed regular presence of clayey matter enclosed in framboidal pyrite, as well as in crystals with
voids and abrupt growth layers. The EF patterns were plotted for average TE (Figure 14) normalised
to the Al content which was determined at each point (EFelement =
([C]element/[C]Al)sample/([C]element/[C]Al)lithogenic) [45]. Their shapes changed slightly relative to the bulk
fraction spectra (Figures 13 and 14) because LA-ICPMS determined additionally Se, Ag, Sn, Re, Tl,
and Bi but did not uncover Hg. Nevertheless, framboidal pyrites from Andrusov and Tischenko
Hills preserve the shapes of their EF patterns, with Mn, Co, Ni, and Cu enrichment in framboids, all
Minerals 2018, 8, 344 24 of 40

about EF = 103–104 (peak I); high enrichment in As, Se, and Mo in both framboids (EF = 10 4–105) and
crystals (EF to 103–104), peak II; Re enrichment (EFRe ~104–105 in framboids and EFRe ~103–104 in
crystals) forms peak III. The Zn minimum is distinct in all analysed samples (EF ~101–103). Figure 14
clearly shows that pyrite framboids lose all impurity types when recrystallise to crystals in the
Andrusov and Tischenko samples, with the greatest decrease in Mn, Cu, Zn, Ag, and Au (two or
three orders of magnitude). Unlike these, the crystals and the framboids from Trubetskoy Hill
contain similar concentrations of most TE (Mn, Co, Ni, Cu, As, Mo, Cd, and Tl), and the crystals are
enriched in Zn, Se, and Au. We attribute this effect to uptake of foreign inorganic particles by
rapidly growing defect crystals which are abundant in the sample (Figure 8b).
The TE composition of marcasite was studied only in the Andrusov Hill sample where the
mineral is relatively common. The pyrite and marcasite crystals have similar EF patterns but the
latter are markedly depleted in Mo and Re (Table 8) and have a high value of EFAg ~103 (Figure 14).
All analysed pyrites show 34S depletion relative to seawater sulphate (about +20‰) [42] (Figure
15). The δ34Spyrite compositions are the lightest in the Tischenko samples (+0.4‰ and −1.5‰ for
framboids and +0.4‰ for crystals), the heaviest in Andrusov Hill (+8.9‰ and +8.2‰, respectively),
and intermediate in Trubetskoy Hill (+5.7‰ and +7.4‰ for framboids and +4.0‰ for crystals).

Table 7. Trace element composition of pyrite framboids from mud masses, Bulganak MV area,
Kerch-Taman MV province. LA-ICPMS data, ppm.

Location Andrusov Hill Trubetskoy Hill Tischenko Hill

Element Mean (n = 23) Min Max Mean (n = 12) Min Max Mean (n = 16) Min Max
Al 32.8 0.20 271 91.9 18.8 231 98.0 0.96 248
Ti 2.80 0.27 14.7 11.9 1.72 37.8 6.97 0.44 34.7
Mn 1209 67.7 3654 958 78.5 2323 1853 351 5715
Co 79.3 0.23 355 141 0.8 345 46.1 1.03 206
Ni 116 5.76 438 383 1.61 714 140 2.98 392
Cu 123 1.34 1004 842 23.9 1656 203 6.23 678
Zn 30.3 2.18 87.9 18.9 6.96 33.1 32.2 6.25 60.1
As 248 3.74 1466 164 6.84 262 148 12.1 526
Se 7.67 0.85 22.3 11.7 3.63 26.8 10.1 1.91 37.8
Zr 0.42 0.11 1.79 0.57 0.33 1.06 0.93 0.08 2.81
Mo 6.55 0.08 35.3 3.67 0.33 8.91 10.7 0.15 48.4
Ag 0.43 0.01 3.19 2.19 0.61 3.93 0.82 0.02 3.24
Cd 0.08 0.01 0.39 0.17 0.12 0.21 0.13 0.01 0.33
Sn 0.34 0.13 1.06 6.59 0.19 25.2 0.28 0.13 0.44
Sb 1.44 0.06 2.82 2.28 1.12 3.94 2.72 0.13 6.75
Te 0.46 0.05 1.37 0.58 0.48 0.68 0.89 0.12 2.33
Ce 0.12 0.002 0.45 0.17 0.02 0.26 0.25 0.01 0.93
Re 0.04 0.002 0.11 0.005 0.002 0.007 0.02 0.001 0.05
Au 0.02 0.004 0.06 0.02 0.01 0.05 0.02 0.01 0.03
Tl 3.70 0.27 14.1 2.69 1.28 5.15 1.34 0.11 3.42
Pb 47.8 0.12 511.6 250 2.68 664 68.9 2.63 207
Bi 0.24 0.004 2.84 1.72 0.83 3.45 0.23 0.01 0.42
Re/Mo 0.006 0.001 0.002
Te/Se 0.06 0.05 0.09
Sb/Se 0.19 0.19 0.27
Tl/Se 0.48 0.23 0.13
n = number of analyses.
Minerals 2018, 8, 344 25 of 40

Table 8. Trace element composition of pyrite and marcasite crystals from mud masses, Bulganak MV
area, Kerch-Taman MV province. LA-ICPMS data, ppm.

Location Tischenko Hill Andrusov Hill Trubetskoy Hill

Ineral Pyrite Pyrite Marcasite Pyrite
Mean Mean Mean
Element Mean (n = 11) Min Max Min Max Min Max Min Max
(n = 13) (n = 10) (n = 10)
Al 760 2.7 2029 62.6 25.5 91.1 214 10.8 777 35.0 0.40 99.1
Ti 86.5 2.7 257 10.2 1.95 17.9 25.7 4.68 38.5 8.22 0.39 32.7
Mn 2012 12.3 6208 13.1 0.67 64.8 72.5 1.93 215 215 3.93 434
Co 8.69 1.81 86.4 6.15 0.25 28.5 10.3 0.59 20.0 3.11 1.57 7.87
Ni 14.2 4.52 271 42.8 0.84 176 15.5 1.07 36.8 8.70 2.60 18.6
Cu 112 3.19 647 16.7 0.93 32.5 1.86 0.81 2.91 39.2 1.68 82.2
Zn 76.9 1.62 296 8.16 0.51 26.7 6.29 0.66 14.8 17.2 1.21 41.1
As 490 3.10 933 1034 0.33 2104 278 0.23 865 23.1 2.71 60.3
Se 13.4 4.15 46.1 10.2 3.30 18.2 46.5 46.5 46.5 9.42 1.51 17.5
Zr 6.12 0.16 23.9 0.17 0.07 0.36 0.63 0.03 1.62 0.14 0.04 0.29
Mo 45.4 0.35 121 204 0.03 539 15.5 0.02 61.3 7.56 0.34 18.5
Ag 2.80 0.03 10.3 0.10 <0.02 0.12 0.07 <0.02 0.09 0.10 0.03 0.16
Cd 0.29 0.01 0.45 0.10 0.04 0.22 0.03 0.01 0.05 0.02 <0.01 0.03
Sn 0.35 0.21 0.48 0.23 0.20 0.25 0.20 <0.12 0.24 0.28 0.20 0.39
Sb 13.1 0.27 54.0 22.3 1.46 49.0 1.74 0.02 6.41 1.41 0.20 2.77
Te 6.65 1.93 6.87 <0.04 <0.04 <0.04 <0.04 <0.04 <0.04 0.02 <0.01 0.08
Ce 0.92 0.01 3.25 0.06 0.02 0.15 0.36 0.02 0.99 0.04 0.01 0.07
Re 0.01 0.004 0.05 0.004 0.001 0.007 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01
Au 0.02 0.01 0.03 0.007 0.003 0.02 0.01 0.004 0.01 0.01 0.01 0.01
Tl 1.21 0.01 2.37 2.64 0.05 5.22 1.31 0.04 4.70 3.17 0.67 6.4
Pb 249 2.46 1083 11.5 0.22 54.60 2.37 0.40 7.37 2.11 0.40 5.06
Bi 0.25 0.01 1.06 0.17 0.02 0.32 0.01 0.004 0.01 0.01 0.004 0.038
n = number of analyses.
Minerals 2018, 8, 344 26 of 40

Figure 14. Incorporation of trace elements in different textural forms and polymorphic modifications
of FeS2. LA-ICPMS analyses of pyrite and marcasite (Tables 7 and 8). Relative enrichment factor:
EFelement = ([C]element/[C]Al)sample/([C]element/[C]Al)PAAS [45]. PAAS after [75]. (a) Tischenko hill, (b)
Andrusov hill, (c) Trubetskoy hill.
Minerals 2018, 8, 344 27 of 40

Figure 15. Trace element loading (a) and stable sulphur isotope composition (b) of pyrite from the
MMS. ME = V + Cr + Mn + Co + Ni + Cu + Zn + Mo + Cd + Sb + Au + Pb. Sulphur isotope composition
of sea water sulfate after [42].

4.3.4. Host Minerals for Hg, Zn, Cu, Pb, Ag, Au

Cinnabar, sphalerite and akantite were found in the sulphide concentrate from Andrusov Hill,
whereas Cu–Fe and Pb sulphides, native Cu, Au and (Au, Ag) alloys were found in Tischenko Hill
(Figure 12).
Cinnabar mainly occurs as massive aggregates of anhedral micrograins with trigonal etch pits;
less often it forms subhedral grains with sharp edges and corners and even perfect crystals with
pinacoidal and rhombohedral faces (Figure 12c). Cinnabar corresponds to the Hg0.97S1.03 composition
(85.42–85.68 wt % Hg and 14.41–14.87 wt % S) with patchy distributions of Cu (1.05 wt %), Fe (0.94
wt %), and Zn (up to 0.38 wt %), which may indicate the presence of finest inclusions of the
respective sulphides.
Sphalerite occurs as straw yellow tetrahedrons, up to 200 µm in size (Figure 12d), and has sharp
edges and corners and complex microtopography of face surfaces with numerous abrupt growth
layers. The mineral contains Zn (65.42–65.84 wt %), Fe (0.34–0.55 wt %) and S (32.71–33.15 wt %)
corresponding to the formula Zn0.97Fe0.01S1.00. Other TE concentrations (Cd, Cu, As, Sb) are below the
EMPA detection limits.
Cu–Fe sulphides (chalcopyrite and nukundamite) were found inthergrown (Figure 12a,b).
Chalcopyrite occurs as 5–20 µm tetrahedrons. The EMPA data (29.80 wt % Fe, 33.47 wt % Cu, 34.81
wt % S and 1.17 wt % As) lead to the formula Cu0.98Fe0.99S2.01As0.03. Another Cu–Fe sulphide exists as
reniform aggregates (with spheroids 10–25 µm in diameter) consisting of numerous 1–2 µm stellar
microcrystals (twins or skeletal forms?). Its composition (56.18–56.64 wt % Cu, 8.56–8.90 wt % Fe,
and 34.26–34.23 wt % S; Cu5.04Fe0.89S6.07) corresponds to nukundamite (Cu5FeS6) [85,86].
Akantite (α-Ag2S) was found only once as flakes on the pyrite crystals surface (Figure 12i).
Pb Sulphide was found as a single tiny (~1 µm) particle hosted by a fine-grained aggregate with
Fe-rich carbonate, gypsum and Fe-(oxy)hydroxides.
Minerals 2018, 8, 344 28 of 40

Gold and gold-silver alloys mainly occur as massive, lumpy, or flattened 30–150 µm particles
(60–80 µm in average). Gold particles bear neither signatures of wear and long distance transport,
nor etch grooves and pits which would indicate dissolution under supergene conditions. The
surfaces of a few gold particles are decorated with later pancake-like overgrowths. They vary in
fineness from 736 to 1000, higher in the rims (~890–990) and in the pancake-like overgrowths (~995).
The cores are richer in Ag (~800–950) (Figure 12g,h), but traces of copper (0.6–1.0 wt %) are restricted
to the rims.
Metallic copper occurring as thin (~10 µm) foil was found aggregated with quartz, albite, and
pyrite crystals (Figure 12e,f).

5. Discussion

5.1. Provenance of the Middle Maykopian Sedimentation in the Western Termination of the Indol-Kuban
Trough: Mineralogical Evidence
The mineralogy and abundance of clastic (including HM) and clay minerals have implications
for the provenance, deposition environments, weathering, diagenesis, and palaeogeography. The
MMs from the Bulganak MV field are mainly composed of sandy illite clay with relatively high
kaolinite and low mix illite-smectite percentages, which records diagenetic alteration of primary
mud in a buried zone. More rigorous constraints on the burial depth based on illite/smectite ratios
are beyond the scope of this paper, but we will discuss the potentialitiy and limitations of
illite-smectite thermometry.
The illite/smectite ratio and the vitrinite reflectance (R0) are useful indicators of sediment
maturation degree as both are irreversible and record the maximum temperature ever attained by
the rocks. These parameters allow plotting temperature variations for specific basins when used
jointly [87,88], but the illite/smectite ratios alone cannot provide precise thermometric constraints.
Although there exist numerous thermodynamic models and data characterising low-temperature
phyllosilicates, as well as experimental constrains on their phase-temperature relationships, no
direct reaction bracketing is available, because the kinetics of illite-to-smectite transition is too
sluggish below 200 °С [89]. As shown by detailed mineralogical and experimental studies,
illite-to-smectite transition is not a simple dehydration reaction mainly controlled by equilibrium but
a complex process involving progressive conversion of smectite to illite accompanied by change of
Si:Al:K stoichiometry [89] or Fe reduction at octahedral sites leading to increased layer charge,
coupled with K fixation [90]. The K-rich pore fluid in shales tends to buffer illite within its stability
field, and illitisation can be treated as a kinetic process mostly occurring in the temperature range
from 70 to 130 °С [89,91]. The conversion proceeds via increase in illite contents in mix illite-smectite
from ~20% to ~80%, and is the fastest between 90 and 120 °С [91]. The mix illite-smectite phases in all
analysed Bulganak MM samples contain about 70% of illite layers, i.e., the primary marine
sediments experienced diagenetic alteration at 80 to 100 °С. These estimates are consistent with fluid
generation temperatures (ТMg/Li) from 76 to 117 °С and suggest the presence of a mud reservoir at a
depth of 2.5–3.5 km. The Bulganak MVs extrude fluidised mature shales mobilised from the lower
Middle Maykop section. The expelled aqueous fluids are mature pore waters that formed when
saline sea water buried together with primary smectite-dominated mud mixed up with fresher B-
and Li-rich waters released by smectite dehydration.
High contents of kaolinite and low percentages of non-resistant minerals (chlorite, muscovite,
epidote and amphibole) in the MM and Middle Maykop Shale samples indicate that clastic inputs to
the western termination of the Indol-Kuban Trough were mostly from mature kaolinite weathering
profiles in the Russian Platform [52]. All HM ultrastable assemblages consist of abundant rutile,
ilmenite, sillimanite, kyanite, (±andalusite), and garnet with minor tourmaline, zircon, titanite, and
apatite. They comprise diverse index phases mainly derived from peraluminous high-grade
metamorphic and granitic rocks and represent clastic inputs from the Ukrainian shield. The
roundness of ultrastable HM grains indicates distant clastic transportation by large river systems
(paleo-Don, paleo-Kuban, etc.) [52,54,55]. The Caucasian mountain system was the provenance for
Minerals 2018, 8, 344 29 of 40

assemblages of scarce non-resistant minerals (epidote, pyroxene, amphibole, and chlorite).

Therefore, the contribution of the southern provenance into the western Indol-Kuban Trough was
limited during the Middle Maykopian sedimentation. The Middle Maykop Shales contain more
non-resistant minerals than the Bulganak MMs because the Taman Peninsula is closer to the
Caucasus than the Kerch Peninsula (Figure 1).

5.2. Main Trends of Trace Element Sequestration by Mineral Hosts in Oxygen-Deficient Environments

5.2.1. Geochemical Fingerprints of Carbonates

Commonly most reactive Fe and Mn enter deep-water marine sediments as a very fine-grained
Fe3+- and Mn4+-(oxy)hydroxides [92], which is also the case for the analysed sediments. During
diagenesis in oxygen-deficient environments, Mn4+-(oxy)hydroxides underwent early reduction
which precedes both Fe3+ and sulphate reduction and the related production of H2S [93,94]. Almost
all Mn2+ reduced from Mn4+ and Mn3+ enters the pore solution and then precipitates as carbonates
[41,77,92], while a considerable part of iron still remains in Fe 3+-(oxy)hydroxides and Fe3+-bearing
layered silicates. Indeed, all studied MM samples contain Fe-(oxy)hydroxides, illite and glauconite,
are free from Mn-(oxy)hydroxides, but contain diverse Mn-bearing carbonates (Figure 10; Table 3).
The members of the MnCO3–CaCO3, CaMn(CO3)2–CaMg(CO3)2, and FeCO3–MnCO3 series were
previously recognised as the major sink of Mn2+ in anoxic sediments [77,95,96]. Romanek et al. [77]
also inferred that metastable mix carbonates may be another significant Mn sink in marine
sediments. Our discovery of natural Mn-bearing mix carbonates in the Maykop Shales supports this
idea. Under weakly reducing conditions in suboxic but non-sulphidic environments, most Mn is
stored in carbonate sinks immediately before the formation of sulphides. As a result, early
framboidal pyrite grows from a medium depleted in Mn2+.
Since the reduction of Fe3+ to Fe2+ requires a higher reducing potential than that of Mn3+(4+) →
Mn [93,94], it would be reasonable to expect regeneration or overgrowing of early Mn-rich
2+

carbonates by later Fe-rich ones. However, we failed to find any zoned carbonate grains with
Mn-rich cores and Fe-rich rims, but found persistent coupling of fine-crystalline intergrowths of
siderite with Fe-(oxy)hydroxide clots, and only mix carbonates beyond these aggregates. This
distribution of numerous fine siderite crystals (Figure 6b) indicates mass nucleation of FeCO3 and
proves that supersaturation with respect to Fe2+ is restricted to the pore solution volume, namely, to
thin films enveloping Fe-(oxy)hydroxides clots.
Earlier experiments of Romanek et al. [77] in the system FeCO3–MgCO3–CaCO3 showed siderite
to grow most rapidly among other Fe-bearing carbonates (at T = 25–250 °С). Precipitation of
Mg-siderite is indicative of very high Mg/Fe ratios (≥10) in the growth medium, while the
incorporation of Mg into the FeCO3 structure slows down considerably the precipitation kinetics. In
the same way, (Fe,Ca)CO3 carbonates, rather than siderite and calcite, preferably grow from
solutions with Ca/Fe molar ratios of 0.03 to 1.11. Precipitation of calcite, in turn, is inhibited by high
Mg concentrations in seawater, also leading to the growth of mix carbonates [77]. Thus, Fe2+
concentration in pore water decreased while the contents of main seawater cations (Mg and Ca)
increased in immature sediments away from the primary storages of highly-reactive iron, which
retarded the siderite nucleation and led to the growth of larger crystals of Mg-siderite and other mix
carbonates. Temperature is another key control of their compositions: as the temperature falls from
70 °С to 25 °С, Mg–Ca siderite, instead of Ca–Fe magnesite, precipitates from Fe2+-, Mg2+-, and
Ca2+-bearing solutions supersaturated with respect to magnesite (Ωmag = 170) [77].
Thus, mix carbonates formed during early diagenesis of the Middle Maykop shales under
control of several factors: (1) availability of highly-reactive (mainly amorphous)
Fe(Mn)-(oxy)hydroxides; (2) seawater composition with Mg strongly exceeding the concentrations
of other cations [97]; (3) suboxic or weakly reducing conditions, optimal for outpacing reduction of
Mn4+ and restricted reduction of Fe3+; (4) low temperatures (of about 8 °С) of bottom water and
subbottom mud. The joint action of these (mainly kinetic) factors made mix cation carbonates (along
with siderite) the principle Fe sinks in oxygen-deficient (or weakly sulphidic) environments.
Minerals 2018, 8, 344 30 of 40

Both bulk Fe-rich fractions of authigenic carbonates and their individual crystals showed Zn
enrichment (up to 0.2 wt % ZnO). Possible mechanisms of Zn and Cd accumulation in marine
carbonates have been discussed in our recent publication [47]. According to the model of Zn
co-precipitation with CaCO3 [98], zinc appears to remain on the calcite surface as hydrated
complexes or as Zn5(OH)6(CO3)2 (hydrozincite) films, which may incorporate into calcite by
recrystallisation due to low solubility of hydrozincite (Ksp = 10−14.9 at 25 °С) [99]. Thus, a large part of
Zn resided in carbonates early during diagenesis already, under weakly reducing conditions, and
thus could not contribute to later precipitation of sulphides triggered by sulphate reduction.
Diagenetic carbonate growth has been unanimously recognised to be a single-event process
occurring early during diagenesis. Carbonates grow in sediments at shallow burial depths below the
seafloor; they commonly survive themselves and preserve their geochemical fingerprints even in old
rocks spared by metamorphism [80,100]. There are three distinct depositional environments that
may lead to precipitation of Fe(±Mn)-rich carbonates [41,101]: (1) suboxic diagenesis in slowly
deposited pelagic sediments with low concentration of organic matter, an optimal environment for
siderite precipitation; (2) suboxic Fe(Mn)-(oxy)hydroxide reduction and microbial methanogenesis
under unlimited inputs of highly reactive iron, at shallow burial depths below the seafloor, favorable
for precipitation of Fe- and Mn-carbonates; (3) reduction of sulphate and Fe3+ (at a rate that balances
or exceeds the sulphate reduction rate), which can maintain co-precipitation of Fe-rich carbonates
and Fe sulphides, if reactive iron is available.
Abundant Fe(Mn)- and mix carbonates coexisting with relatively scare FeS 2 in the samples we
studied, as well as their concordantly changing trace element and isotopic patterns, suggest a
syngenetic origin early during diagenesis of the Middle Maykop shales, by scenario (3). Depletion of
the analysed authigenic carbonates in both 12C and 16O relative to their marine counterparts from the
zone of active sulphate reduction and microbial methanogenesis [41] points to a mineral-forming
medium rich in (SO4)2−, at lower organic carbon contents in the sediment, and inhibited
sulphate-reducing activity and methanogenesis. Judging by the narrow δ 13C range (δ13C = +2.1 to
+3.7‰ VPDB), most of carbon in the carbonates came from a single seawater inorganic source (δ 13C =
−2 to +2‰ VPDB), without inputs of oxidised organic matter (δ 13C~−25‰ VPDB) and/or methane
(δ13CHCO3~< −75‰ VPDB) [102]. The enrichment of siderite in 18O relative to the coexisting mix
carbonates may also indicate a contribution from an 18O-enriched source, possibly associated with
18O-rich pore water and/or dissociation of gas hydrates [103,104]. An assemblage similar to that we

studied (Fe(oxy)hydroxides + FeS2 + Fe–Mn carbonates + barite-celestine) was recently shown [104]
to be a single mineral complex that formed during early diagenesis of marine sediments at
decomposition of methane hydrate.
Authigenic carbonates are most often compositionally homogeneous, while zoned, regenerated,
and recrystallised Fe–Mn- and mix authigenic marine carbonates are very rare. One such example
was described by Chow et al. [41], who suggest that continuous crystal growth, with composition
change upon burial, was possible due to high pre-cement porosity of the sediments. Note that
authigenic carbonates in the studied MMs do not show aligned/flattened intergrowths and zoned
crystals, the structures of overgrowth, regeneration, and/or replacement of earlier carbonates by
later generations, or partial dissolution of crystals. Judging by the absence of all these signatures,
carbonate precipitation in the sediment in our case was rather a single event that most likely
predated compaction. It is most likely kinetic rather than thermodynamic factors that impeded the
growth of authigenic carbonates in the Maykop shales. Their individual grains became encapsulated
in compact clayey coat, which blocked the exchange processes already during early diagenesis, due
to low permeability of shales which progressively increased with depth.

5.2.2. Trace Element Composition of Sedimentary FeS2 and TE Partitioning during Diagenesis
TE concentrations in sedimentary pyrite track the primary elemental abundance in coeval
seawater. Thus, pyrite of any Cenozoic marine sediment is enriched in the same TE elements as the
current oxygenated ocean: Mo, As, Ni, Zn, Cu, Se [81]. Indeed, pyrites in the MMs we studied show
Mo, As, Ni, Cu, and Se peaks (Figure 14) and contain the same amounts (>10 up to <100 ppm) of Cd,
Minerals 2018, 8, 344 31 of 40

Sb, Ag, and Tl as pyrite from any other Cenozoic marine sediments [81]. Moreover, the Kerch-Taman
authigenic pyrites and current seawater have basically similar TE distribution patterns (Figure 16).

Figure 16. Trace element patterns of framboidal pyrite (1) and pyrite crystals (2) from Bulganak MV
area in comparison with sea water (3) [105]. LA-ICPMS data for average composition of pyrites from
Andrusov, Trubetskoy and Tischenko Hills (Tables 7 and 8). TE concentration in sea water is
[C]element·10.

The analysed pyrites differ from others in Zn and Cd depletion, as well as in Pb, Mn and Re
enrichment (Figure 14). Tribovillard [106] considered pyrite to be the main Zn host in
oxygen-deficient sediments and reported zinc incorporation into pyrite by the Zn 2+ → Fe2+
substitution. It occurs as ZnS micro-phases or domains which can co-crystallise with FeS2 or enter
the FeS2 matrix during diagenesis. On the other hand, Zn and Cd in immature recent and
pre-Quaternary sediments were found to form discrete sulphides rather than being incorporated
into pyrite [46,47,107–109]. The presence of sphalerite crystals in MMs is evidence of the latter
scenario of Zn behaviour in the formation of the parent sediments. Furthermore, the prominent Zn
minimum in the EF patterns of the pyrite crystals, framboids, and bulk sulphide fractions (Figures 13
and 14) attests to Zn storage by earlier precipitated authigenic solids, namely carbonates.
Low contents of Cd in all our samples are most likely due to low bioproductivity of the Maykop
stagnant and freshened basin, because biogenic shuttle of Cd to the marine sediments has been its
main source [110,111].
Lead tends to be introduced into marine basin by hydrothermal activity [48]. The water of the
Oligocene-Miocene Indol-Kuban basin apparently received Pb from the Greater Caucasus in the
south, with numerous Pb–Zn deposits [112].
Manganese enrichment of both carbonates and matrix of earlier framboidal pyrites can be
reasonably explained by the lithology of the provenance that supplied sediments to the western
flank of the Indol-Kuban Trough: Oligocene Mn carbonates and their thick eluvium extend, with
some gaps, along the southern slope of the Ukraine shield in a 25 km wide and 250 km long zone
which accommodates the Europe largest Nikopol Mn deposit [113].
Since highly-reactive Fe-(oxy)hydroxides were obviously in excess during the Maykop
deposition, pyrite crystallisation is expected to be limited by local [HS −] concentration. The lower the
[HS−] concentrations, the less pyrite could precipitate and the more TE it captured from the pore
solution [81]. The highest TE sequestration by earlier framboids from Andrusov Hill, along with
Minerals 2018, 8, 344 32 of 40

their heaviest sulphur isotopic composition (δ34S = +8.9‰) and highest Re/Mo ratio, suggest
depressed biogenic reduction of seawater sulphate during their formation. Other framboids result
from prolific microbially mediated sulphate reduction, judging by similar EF patterns, though with
lower absolute TE concentrations, as well as by lighter δ34S contents and lower Re/Mo ratios.
While re-crystallising into both pyrite and markasite crystals, the framboids become depleted in
most TE but retain high As and Mo contents (Figure 14). The SEM data leave no doubt that some TE
(Cu, Ag, Au, Pb) that released during the recrystallisation of framboidal pyrite became then stored in
quite large particles of sulphides, metals or alloys. Other TE may occur as microinclusions in pyrite
crystals, as indicated by their “patchy” distributions revealed by both EMPA and LA-ICPMS (Tables
7 and 8). The amount of impurities the framboidal pyrite loses during re-crystallisation varies in
different samples (Figure 14) and obviously correlates with the type and diversity of coexisting TE
host minerals. This percentage is the highest for the Tischenko Hill pyrites which are mostly
depleted in Cu, Au, Ag and Pb. The respective heavy fraction contains three phases of Cu, Au, (Au,
Ag) alloys and Pb sulphide (Table 3). The Andrusov Hill pyrites have lost a lower amount of
impurities: they are depleted in Ag and Zn, while sphalerite, akantite and cinnabar are present in the
sulphide concentrate (Figures 12 and 14; Table 3). The contents of most TE in the pyrite crystals and
framboids from the Trubetskoy Hill sample are commensurate, but the crystals have greater Se, Mo
and Mn enrichments than the framboids (Figure 14). However, this may be a false effect rather
associated with defects and occluded solid inclusions in pyrite crystals (Figure 8). No TE hosts other
than FeS2 have been found in the sample.
The fate of Zn, Cd, Cu and Hg during the evolution of authigenic sulphides under
oxygen-deficient conditions requires separate consideration. As suggested by Morse and Luther
[92], there are not only thermodynamic but also kinetic prerequisites for the formation of different
TE-hosts in sediments deposited under oxygen-deficient conditions. Faster water exchange reaction
kinetics for Pb, Zn, and Cd than for Fe2+ explains why MeS phases (Me = Pb, Zn, Cd) precipitate
faster and prior to pyrite, whereas Co and Ni, which have slower H 2O exchange kinetics than Fe2+,
are commonly incorporated into pyrite. Although Cu2+ has higher water exchange rates than Fe2+,
this element commonly shows intricate behaviour in sulphidic sediments because it exists in both +2
and +1 oxidation states. In suboxic environments, Cu can incorporate into pyrite as impurity, form
other sulphides, or occur as complex compounds (chelates) in the sediment [44,92,107,114]. Indeed,
Cu in the samples we studied does show the most complicated speciation: it resides in pyrite and
marcasite, forms chalcopyrite and nukundamite, occurs as metallic copper or as impurity in (Au,
Ag) alloys.
Mercury, with its water exchange rate higher than in Fe, was expected to form its own mineral
prior to FeS2 formation [92]. On the other hand, Hg shows the strongest chloride complexation and
highest hydrolysis constant, which should retard its reactivity with [HS −] and allow incorporation of
Hg into FeS2. Previously, sequential extraction results for anoxic marine sediments led Huerta-Diaz
and Morse [107] to infer that all Hg could reside in pyrite. We have not seen published evidence of
Hg capability to form its own phases during diagenesis. Possibly, the discovery of cinnabar crystals
in the Maykop Shales is the first find of this kind.
Unfortunately, we failed to find pyrite intergrown with other sulphides but Ag 2S, which would
provide an explicit record of the crystallisation sequence. However, purification of pyrite crystals
from most TE impurities we observed is evidence of conditions favourable for the growth of
authigenic sulphides, as well as metallic species and alloys, both before and after the crystallisation
of framboidal pyrite.
According to the criteria suggested by Large et al. [115], the Maykop sedimentary pyrites may
be classified as diagenetic arsenian with refractory (dissolved) gold. Given that the pyrites contain
no more than 0.06 ppm Au, the Oligocene-Miocene sediments of the Indol-Kuban Trough are
unproductive [115]. Nevertheless, pyrite recrystallisation was accompanied by purification from the
Au impurity and formation of free gold particles.
Minerals 2018, 8, 344 33 of 40

5.3. Degree of Anoxia/Oxygenation in Sediments: Mineralogical and Geochemical Constraints

The data on the authigenic mineral assemblages of the studied MMs can place more rigorous
constraints on the degree of anoxia during the parent rocks deposition. The predominance of
Fe(Mn)-carbonates over FeS2 phases indicates transitional suboxic-to-anoxic depositional
environments [48,94]. At significant inputs of highly reactive Fe (oxy)hydroxides into bottom
sediments, the precipitation of Fe and/or Mn carbonates was mainly governed by active (unchelated)
metals in the pore solutions whereas the crystallisation of sulphides was very likely limited by local
concentrations of microbially-produced sulphidic sulphur. The environmental conditions during the
precipitation of Fe(Mn) carbonates were weakly reducing but non-sulphidic, according to the
classification in [46]. Oxygen depletion occurs in subbotom mud but sulphate reduction has not
completed yet. Berner [116] estimated such conditions numerically as [O 2] < 10−6 mol/L and [H2S] <
10−6 mol/L.
TE pyrite composition can be used as effective proxy for anoxia estimations [48,81], namely, Re,
Se, Te with marked storages in the analysed pyrites, are proxy of environment
oxygenation/reduction. According to the criteria of Parnell et al. [48], a Re/Mo ratio of about 0.006
(>0.005) estimated for the Andrusov Hill framboids characterises the host sediments as deposited in
suboxic environments, whereas the lower Re/Mo ratio (<0.002) in the Tischenko Hill framboids
indicates a more reducing environment. Other relative concentrations of redox sensitive elements
such as Te/Se, Sb/Se and Tl/Se (Table 7) in pyrite framboids concordantly decrease from the highest
values in the Andrusov Hill samples to the lowest ones in those from Tischenko Hill. This trend also
reveals [48] the highest degree of pore water oxygenation in the former case and the most reducing
depositional environment in the latter one, with intermediate characteristics for the Trubetskoy Hill
sediments. The δ34S depletion of authigenic pyrite likewise supports its growth under weakly
sulphidic conditions [42,46]. The δ34S decrease from the heaviest in the framboids from Andrusov
Hill (δ34S = +8.9‰) to the lightest in the Tischenko Hill sample (+0.4‰ and−1.5‰ for framboids)
(Figure 15) confirms that framboidal pyrite formed under restricted microbially-induced sulphate
reduction, which was very low in the former case.

6. Conclusions
The obtained data on mineralogy, mineral chemistry, and TE compositions of both bulk
rocks/fractions and separate minerals reveal three mineral assemblages in the mud volcanic ejecta
from the Bulganak field. The three assemblages differ in origin and each bears evidence of the
deposition environments of the parent mudrocks (Miocene Middle Maykop shales), which are
currently extruded by mud volcanoes.
Clay minerals store a record of the provenance of material transported to the sedimentary basin
and the maturity of the currently extruded sediments. High illite/smectite ratios in MMs that
experienced diagenetic alteration at 80–100 °С are consistent with fluid generation temperatures
(ТMg/Li) from 76 to 117 °С. The Bulganak MVs are fed from a mud reservoir located at a depth of
2.5–3.5 km, which corresponds to the depth of the lower Middle Maykop Formation in the
north-eastern Kerch Peninsula. Ultrastable and non-resistant heavy mineral assemblages indicate
the principal and subordinate provenance areas: the Ukrainian shield and the Greater Caucasus,
respectively. High contents of kaolinite also support clastic inputs to the western termination of the
Indol-Kuban Trough mostly from the southern Russian Platform.
The MMs from the Bulganak area are remarkable by diverse authigenic mineralogy: seven
mineral species of carbonates, including complex Fe–Mg–Mn–(Ca) carbonates, eight species of
sulphides, three metallic species (Cu, Au and Au–Ag alloy), quartz, glauconite, and apatite. The
concordant changes of TE compositions and O, C, and S isotopic signatures in the authigenic
carbonates and sulphides confirm their syngenetic origin. We checked several geochemical criteria
which strongly indicate that the authigenic assemblages formed during early diagenesis under
suboxic depositional conditions in a (SO4)2−-rich medium, at suppressed sulphate reduction and
inhibited methanogenesis. These conditions were favorable for complete Mn 3(4)+ to Mn2+ reduction
Minerals 2018, 8, 344 34 of 40

followed by partial reduction of Fe3+ to Fe2+, and subsequent Fe(Mn)-rich carbonate precipitation
before sulphate-reduction and Fe sulphide formation. The co-precipitation of predominant
Fe(Mn)-rich carbonates with lesser amounts of TE-enriched Fe sulphides inferred for the Bulganak
MMs is common to the settings of sufficient reactive iron supply and Fe 3+ reduction at rates faster
than sulphate reduction [101]. This highly TE loaded pyrite incorporates the same TE elements (Mo,
As, Ni, Cu, Se, Re, Sb, Tl) as the Cenozoic oxygenated ocean [81]. During sediment maturation,
earlier pyrite framboids recrystallise and loose TE, which than become stored as sulphides, metals or
alloys. Thus the above physicochemical conditions, together with kinetic factors, are jointly
responsible for the diverse authigenic mineralogy of the extruded mud masses.
We failed to find any solids produced by reactions of described authigenic minerals with very
specific (Na-, Cl-, B-, and Li-rich) MV aqueous fluids. Possible reasons are: (1) low water/rock ratios
and very low porosity of mud masses; (2) encapsulation of individual authigenic mineral grain in
compact clayey coats; (3) short duration of water-rock interaction during MMs ascent and extrusion.
The mineral-forming potential of MV aqueous fluids can fully realise only upon abrupt changes of
physicochemical conditions when fluid are expulsed to the surface. MV fluids can generate very
specific mineral assemblages of salt crusts rapidly growing on the evaporation barrier.

Supplementary Materials: The following are available online at www.mdpi.com/xxx/s1, Table S1: The
supplementary information details the LA-ICPMS analytical method for in situ FeS2 analysis.

Author Contributions: Project idea: E.S., S.K., O.K.; Mineralogy and petrography: E.S., S.K. and S.N.; Field
work: E.S., S.K., S.N. and M.K.; EPMA analyses: E.N.; Writing: E.S., S.K., O.K., and S.N.; ICP-MS analysis and
preconditioning of samples: O.K.; XRD analysis, and preconditioning of samples, and interpretation: P.K. and
E.B.

Funding: This research was funded by the Russian Science Foundation, grant number 17-17-01056

Acknowledgments: The manuscript benefited much from the thoughtful review and valuable comments by
anonymous reviewers. We kindly appreciate the fruitful scientific collaboration of our colleagues from the
Department of Marine Geology and Sedimentary Ore Formation, NAS of the Ukraine (Kiev, Ukraine) and
personally academician Ye.F. Shnyukov. We would like to thank V.S. Kamenetsky (School of Physical Sciences
University of Tasmania, Hobart, Australia) and C. März (University of Leeds, UK) for constructive criticism of
the initial manuscript version, valuable comments and their helpful suggestions. We further thank T.
Perepelova as well as M. Khlestov (IGM, Novosibirsk) for their helpful advice to the present work. We kindly
appreciate Ivan Belousov (ARC Centre of Excellence in Ore Deposits (CODES), University of Tasmania, Hobart,
Australia) for the LA-ICPMS analyses of pyrite. The study was supported by the Russian Science Foundation,
grant 17-17-01056.

Conflicts of Interest: The authors declare no conflict of interest.

References
1. Rakhmanov, R.R. Mud Volcanoes and Their Petroleum Potential; Nedra: Moscow, USSR, 1987. (In Russian)
2. Kopf, A. Significance of mud volcanism. Rev. Geophys. 2002, 40, 1–52, doi:10.1029/2000RG000093.
3. Shnyukov, E.; Sheremetiev, V.; Maslakov, N.; Kutniy, V.; Gusakov, I.; Trofimov, V. Mud Volcanoes of the
Kerch-Taman Region; GlavMedia Publishing House: Krasnodar, Russia, 2005. (In Russian)
4. Evans, R.J.; Davies, R.J.; Stewart, S.A. Internal structure and eruptive history of a kilometre-scale mud
volcano system, South Caspian Sea. Basin Res. 2007, 19, 153–163, doi:10.1111/j.1365-2117.2007.00315.x.
5. Alizadeh, A.A. Geology of Azerbaijan, Oil and Gas, v. VII; Nafta-Press: Baku, Azerbaijan, 2009. (In Russian)
6. Mazzini, A. Mud volcanism: Processes and implications. Mar. Pet. Geol. 2009, 26, 1677–1680,
doi:10.1016/j.marpetgeo.2009.05.003.
7. Dimitrov, L. Mud volcanoes as the most important pathways for degassing deeply buried sediments. Earth
Sci. Rev. 2002, 59, 49–76, doi:10.1016/S0012-8252(02)00069-7.
8. Planke, S.; Svensen, H.; Hovland, M.; Banks, D.A.; Jamtveit, B. Mud and fluid migration in active mud
volcanoes in Azerbaijan. Geo-Mar. Lett. 2003, 23, 258–268, doi:10.1007/s00367-003-0152-z.
9. Martinelli, G.; Panahi, B. Mud Volcanoes, Geodynamics and Seismicity; Springer: Dordrecht, The Netherlands,
2005.
Minerals 2018, 8, 344 35 of 40

10. Deville, E.; Guerlais, S.H. Cyclic activity of mud volcanoes: Evidences from Trinidad (SE Caribbean). Mar.
Pet. Geol. 2009, 26, 1681–1691, doi:10.1016/j.marpetgeo.2009.03.002.
11. Bonini, M.; Mazzarini, F. Mud volcanoes as potential indicators of regional stress and pressurized layer
depth. Tectonophysics 2010, 494, 32–47, doi:10.1016/j.earscirev.2012.09.002.
12. Feyzullayev, A.A. Mud volcanoes in the South Caspian basin: Nature and estimated depth of its products.
Nat. Sci. 2012, 4, 445–453, doi:10.4236/ns.2012.47060.
13. Bonini, M.; Tassi, F.; Feyzullayev, A.A.; Aliyev, C.S.; Capecchiacci, F.; Minissaleet, A. Deep gases
discharged from mud volcanoes of Azerbaijan: New geochemical evidence. Mar. Pet. Geol. 2013, 43,
450–463, doi:10.1016/j.marpetgeo.2012.12.003.
14. Chao, H.C.; You, C.F.; Liu, H.C.; Chung, H.C. The origin and migration of mud volcano fluids in Taiwan:
Evidence from hydrogen, oxygen, and strontium isotopic compositions. Geochim. Cosmochim. Acta 2013,
114, 29–51, doi:10.1016/j.gca.2013.03.035.
15. Li, N.; Huang. H.; Chen, D. Fluid sources and chemical processes inferred from geochemistry of pore
fluids and sediments of mud volcanoes in the southern margin of the Junggar Basin, Xinjiang,
northwestern China. Appl. Geochem. 2014, 46, 1–9, doi:10.1016/j.apgeochem.2014.04.007.
16. Oppo, D.; Capozzi, R.; Nigarov, A.; Esenov, P. Mud volcanism and fluid geochemistry in the Cheleken
peninsula, western Turkmenistan. Mar. Pet. Geol. 2014, 57, 122–134, doi:10.1016/j.marpetgeo.2014.05.009.
17. Kokh, S.N.; Sokol, E.V.; Dekterev, A.A.; Kokh, K.A.; Rashidov, T.M.; Tomilenko, A.A.; Bul’bak, T.A.;
Khasaeva, A.; Guseinov, A. The 2011 Strong Fire Eruption of Shikhzarli Mud Volcano, Azerbaijan: A Case
Study with Implications for Methane Flux Estimation. Environ. Earth Sci. 2017, 76, 701,
doi:10.1007/s12665-017-7043-5.
18. Sokol, E.V.; Kokh, S.N.; Kozmenko, O.A.; Lavrushin, V.Y.; Kikvadze, O.A. Mud volcanoes as important
pathway for trace elements input to the environment: Case study from the Kerch-Taman province,
Northern Black Sea. In Proceedings of the SGEM 2018: 18th International Multidisciplinary Scientific
GeoConference, Albena, Bulgaria, 2–8 July 2018; pp. 307–322.
19. Aliyev, A.A.; Guliyev, I.S.; Rakhmanov, R.R. Catalogue of Mud Volcanoes Eruptions of Azerbaijan: 1810–2007;
Nafta-Press: Baku, Azerbaijan, 2009.
20. Sokol, E.; Novikov, I.; Zateeva, S.; Vapnik, Y.; Shagam, R.; Kozmenko, O. Combustion metamorphism in
Nabi Musa dome: New implications for a mud volcanic origin of the Mottled Zone, Dead Sea area. Basin
Res. 2010, 22, 414–438, doi:10.1111/j.1365-2117.2010.00462.x.
21. Seryotkin, Y.V.; Sokol, E.V.; Kokh, S.N. Natural pseudowollastonite: Crystal structure, associated
minerals, and geological context. Lithos 2012, 133–135, 75–90, doi:10.1016/j.lithos.2011.12.010.
22. Grapes, R.; Sokol, E.; Kokh, S.; Kozmenko, O.; Fishman, I. Petrogenesis of Na-rich paralava formed by
methane flares associated with mud volcanism, Altyn-Emel National Park, Kazakhstan. Contrib. Miner.
Pet. 2013, 165, 781–803, doi:10.1007/s00410-012-0835-4.
23. Bagirov, E.; Lerche, I. Flame hazards in the South Caspian Basin. Energy Explor. Exploit. 1998, 16, 373–397.
24. Jakubov, A.A.; Grigoryants B.V.; Aliev, A.D.; Babazade, A.D.; Veliev, M.M.; Gadzhiev, Y.A.; Guseinzade,
I.G.; Kabulova, A.Y.; Kastryulin, N.S.; Matanov, F.A.; et al. Mud Volcanism in the USSR Territory and Its
Relation with Petroleum Potential; Elm: Baku, USSR, 1980. (In Russian)
25. Avdusin, P.P. Mud Volcanoes of the Crimea-Caucasian Geological Province. A Petrographic Study; Izd. AS USSR:
Moscow, USSR, 1948. (In Russian)
26. Yassir, N.A. Mud Volcanoes and the Behaviour of Overpressured Clays and Silts. Ph.D. Thesis, University
of London, London, UK, 1989.
27. Mazzini, A.; Etiope, G. Mud volcanism: An updated review. Earth-Sci. Rev. 2017, 168, 81–112,
doi:10.1016/j.earscirev.2017.03.001.
28. Dill, H.G.; Kaufhold, S. The Totumo mud volcano and its near-shore marine sedimentological setting
(North Colombia)–from sedimentary volcanism to epithermal mineralization. Sediment. Geol. 2018, 366,
14–31, doi:10.1016/j.sedgeo.2018.01.007.
29. Aliev, A.A.; Lavrushin, V.Y.; Kokh, S.V.; Sokol, E.V.; Petrov, O.L. Isotopic composition of pyritic sulfur
from the mud volcanic ejecta in Azerbaijan. Lithol. Miner. Resour. 2017, 52, 358–368,
doi:10.1134/S0024490217050029.
30. Aloisi, G.; Bouloubassi, I.; Heijs, S.; Pancost, R.D.; Pierre, C.; Sinninghe Damsté, J.S.; Gottschal, J.C.; Forney,
L.J.; Rouchy, J.M. CH4-consuming microorganisms and the formation of carbonate crusts at cold seeps.
Earth Planet. Sci. Lett. 2002, 203, 195–203, doi:10.1016/S0012-821X(02)00878-6.
Minerals 2018, 8, 344 36 of 40

31. Gontharet, S.; Pierre, C.; Blanc-Valleron, M.M.; Rouchy, J.M.; Fouquet, Y.; Bayon, G.; Foucher, J.P.;
Woodside, J.; Mascle, J. Nature and origin of diagenetic carbonate crusts and concretions from mud
volcanoes and pockmarks of the Nile deep-sea fan (eastern Mediterranean Sea). Deep-Sea Res. Part II 2007,
54, 1292–1311, doi:10.1016/j.dsr2.2007.04.007.
32. Merinero, P.R.; Lunar, H.R.; Martínez, F.J. Mechanisms of trace metal enrichment in submarine,
methane-derived carbonate chimneys from the Gulf of Cadiz. J. Geochem. Explor. 2012, 112, 297–305,
doi:10.1016/j.gexplo.2011.09.011.
33. Wang, S.; Magalhães, V.H.; Pinheiro, L.M.; Liu, J.; Yan, W. Tracing the composition, fluid source and
formation conditions of the methane-derived authigenic carbonates in the Gulf of Cadiz with rare earth
elements and stable isotopes. Mar. Pet. Geol. 2015, 68, 192–205, doi:10.1016/j.marpetgeo.2015.08.022.
34. Carvalho, L.; Monteiro, R.; Figueira, P.; Mieiro, C.; Almeida, J.; Pereira, E.; Magalhães, V.; Pinheiro, L.;
Vale, C. Vertical distribution of major, minor and trace elements in sediments from mud volcanoes of the
Gulf of Cadiz: Evidence of Cd, As and Ba fronts in upper layers. Deep-Sea Res. Part I 2018, 131, 133–143,
doi:10.1016/j.dsr.2017.12.003.
35. Ershov, V.V.; Levin, B.V. New data on the material composition of mud volcano products on Kerch
Peninsula. Dokl. Earth Sci. 2016, 471, 1149–1153, doi:10.1134/S1028334X16110027.
36. Inan, S.; Yalcin, M.N.; Guliev, I.S.; Kuliev, K.; Feizullayev, A.A. Deep petroleum occurrences in the lower
Kura depression, south Caspian Basin, Azerbaijan: An organic geochemical and basin modelling study.
Mar. Pet. Geol. 1997, 14, 731–762, doi:10.1016/S0264-8172(97)00058-5.
37. Feyzullayev, A.A.; Guliyev, I.S.; Tagiyev, M.F. Source potential of the Mesozoice Cenozoic rocks in the
South Caspian Basin and their role in forming the oil accumulations in the Lower Pliocene reservoirs. Pet.
Geosci. 2001, 7, 409–417, doi:10.1144/petgeo.7.4.409.
38. Fowler, S.R.; Mildenhall, J.; Zalova, S.; Riley, G.; Elsley, G.; Desplanques, A.; Guliyev, F. Mud volcanoes
and structural development on Shah Deniz. J. Pet. Sci. Eng. 2000, 28, 189–206,
doi:10.1016/S0920-4105(00)00078-4.
39. Smith-Rouch, L.S. Oligocenee-Miocene Maykop/Diatom Total Petroleum System of the South Caspian
Basin Province, Azerbaijan, Iran, and Turkmenistan. U.S. Geol. Surv. Bull. 2006, 2201, 1–27.
40. Luther, G.W.; Meyerson, A.L.; Krajewski, J.J.; Hires, R. Metal sulfides in estuarine sediments. J. Sediment.
Res. 1980, 50, 1117–1120, doi:10.1306/212F7B94-2B24-11D7-8648000102C1865D.
41. Chow, N.; Morad, S.; Al-Aasm, I.S. Origin of authigenic Mn-Fe carbonates and pore-water evolution in
marine sediments: Evidence from Cenozoic strata of the Arctic Ocean and Norwegian-Greenland Sea
(ODP LEG 151). J. Sediment. Res. 2000, 70, 682–699, doi:10.1306/2DC40930-0E47-11D7-8643000102C1865D.
42. Rickard, D. Sulfidic Sediments and Sedimentary Rocks; Elsevier: Amsterdam, The Netherlands, 2012.
43. Fleurance, S.; Cuney, M.; Malartre, M.; Reyx, J. Origin of the extreme polymetallic enrichment (Cd, Cr, Mo,
Ni, U, V, Zn) of the Late Cretaceous–Early Tertiary Belqa Group, central Jordan. Palaeogeogr. Palaeocl. 2013,
369, 201–219, doi:10.1016/j.palaeo.2012.10.020.
44. Gregory, D.D.; Large, R.R.; Halpin, J.A.; Lounejeva Baturina, E.; Lyons, T.W.; Wu, S.; Danyushevsky, L.;
Sack, P.J.; Chappaz, A.; Maslennikov, V.V.; et al. Trace element content of sedimentary pyrite in black
shales. Econ. Geol. 2015, 110, 1389–1410, doi:10.2113/econgeo.110.6.1389.
45. Little, S.H.; Vance, D.; Lyons, T.W.; McManus, J. Controls on trace metal authigenic enrichment in
reducing sediments: Insights from modern oxygen-deficient settings. Am. J. Sci. 2015, 315, 77–119,
doi:10.2475/02.2015.01.
46. März, C.; Poulton, S.W.; Beckmann, B.; Kuster, K.; Wagner, T.; Kasten, S. Redox sensitivity of P cycling
during black shale formation: Dynamics of sulfidic and anoxic, non-sulfidic bottom waters. Geochim.
Cosmochim. Acta 2008, 72, 3703–3717, doi:10.1016/j.gca.2008.04.025.
47. Sokol, E.V.; Kozmenko, O.A.; Khoury, H.N.; Kokh S.N.; Novikova S.A.; Nefedov, A.A.; Sokol, I.A.; Zaikin,
P. Calcareous sediments of the Muwaqqar Chalk Marl Formation, Jordan: Mineralogical and geochemical
evidences for Zn and Cd enrichment. Gondwana Res. 2017, 46, 204–226, doi:10.1016/j.gr.2017.03.008.
48. Parnell, J.; Perez, M.; Armstrong, J.; Bullock, L.; Feldmann, J.; Boyce, A.J. Geochemistry and metallogeny of
Neoproterozoic pyrite in oxic and anoxic sediments. Geochem. Perspect. Lett. 2018, 7, 12–16,
doi:10.7185/geochemlet.1812.
49. Okay, A.I.; Şengör, A.M.C.; Görür, N. Kinematic history of the opening of the Black Sea and its effect on
the surrounding regions. Geology 1994, 22, 267–270,
doi:10.1130/0091-7613(1994)022<0267:KHOTOO>2.3.CO;2.
Minerals 2018, 8, 344 37 of 40

50. Sidorenko, A.V. Geology of USSR, v. VIII (Crimea); Nedra: Moscow, USSR, 1969. (In Russian)
51. Zonenshain, L.P.; Le Pichon, X. Deep basins of the Black Sea and Caspian Sea as remnants of Mesozoic
back-arc basins. Tectonophysics 1986, 123, 181–240, doi:10.1016/0040-1951(86)90197-6.
52. Nedumov, R.I. Lithology, geochemistry, and paleogeography of Cenozoic deposits in the Caucasus
foothills. Litologiya i Poleznye Iskopaemye 1994, 1, 69–77. (In Russian)
53. Lavrushin, V.Y.; Kopf, A.; Deyhle, A.; Stepanets, M.I. Formation of mud-volcanic fluids in Taman (Russia)
and Kakhetia (Georgia): Evidence from boron isotopes. Lithol. Miner. Resour. 2003, 38, 120–153,
doi:10.1023/A:1023452025440.
54. Popov, S.V.; Rögl, F.; Rozanov, A.Y.; Steininger, F.F.; Shcherba, I.G.; Kováč, M. Lithological-Paleogeographic
Maps of Paratethys. 10 Maps Late Eocene to Pliocene. Scale: 1:5000000; Courier Forschungsinstitut
Senckenberg: Stuttgart, Germany, 2004.
55. Popov, S.V.; Antipov, M.P.; Zastrozhnov, A.S.; Kurina, E.E.; Pinchuk, T.N. Sea-level fluctuations on the
northern shelf of the Eastern Paratethys in the Oligocene-Neogene. Stratigr. Geol. Correl. 2010, 18, 200–224,
doi:10.1134/S0869593810020073.
56. Kopf, A.; Deyhle, A.; Lavrushin, V.Y.; Polyak, B.G.; Gieskes, J.M.; Buachidze, G.I.; Wallmann, K.;
Eisenhauer, A. Isotopic evidence (He, B, C) for deep fluid and mud mobilization from mud volcanoes in
the Caucasus continental collision zone. Int. J. Earth Sci. (Geol. Rundsch) 2003, 92, 407–425,
doi:10.1007/s00531-003-0326-y.
57. Meisner, A.; Krylov, O.; Nemcok, M. Development and structural architecture of the Eastern Black Sea.
Lead. Edge 2009, 28, 1046–1055, doi:10.1190/1.3236374.
58. Römer, M.; Sahling, H.; Pape, T.; Bahr, A.; Feseker, T.; Wintersteller, P.; Bohrmann G. Geological control
and magnitude of methane ebullition from a high-flux seep area in the Black Sea–the Kerch seep area. Mar.
Geol. 2012, 319–322, 57–74, doi:10.1016/j.margeo.2012.07.005.
59. Kokh, S.N.; Shnyukov, Y.F.; Sokol, E.V.; Novikova, S.A.; Kozmenko, O.A.; Semenova, D.V.; Rybak, E.N.
Heavy carbon travertine related to methane generation: A case study of the Big Tarkhan cold spring,
Kerch Peninsula, Crimea. Sediment. Geol. 2015, 325, 26–40, doi:10.1016/j.sedgeo.2015.05.005.
60. Herbin, J.P.; Saint-Germès, M.; Maslakov, N.; Shnyukov, E.F.; Vially, R. Oil seeps from the “Boulganack”
mud volcano in the Kerch Peninsula (Ukraine-Crimea), study of the mud and the gas: Inferences for the
petroleum potential. Oil Gas Sci. Technol. 2008, 63, 609–628, doi:10.2516/ogst:2008008.
61. Olenchenko, V.V.; Shnyukov, Y.F.; Gas’kova, O.L.; Kokh, S.N.; Sokol, E.V.; Bortnikova, S.B.; El’tsov, I.N.
Explosion Dynamics of the Andrusov Mud Vent (Bulganak Mud Volcano Area, Kerch Peninsula, Russia).
Dokl. Earth Sci. 2015, 464, 951–955, doi:10.1134/S1028334X15090123.
62. Nosovsky, M.F. The regional stratigraphic scale of the Maikopian deposits of the Crimea plain.
Geologichesky Zhurnal 2003, 3, 137–145. (In Russian)
63. Seidov, A.G. Lithology of the Maykop Formation in Azerbaijan; Izd. Akademii Nauk Azerbaidzhanskoi SSR:
Baku, USSR, 1962. (In Russian)
64. Lavrushin, V.Y.; Aidarkozhina, A.; Kikvadze, O.E.; Kokh, S.N. Geochemistry of mud volcanic fluids in the
southern West-Kuban Basin: A case study with implication for source and mobilization depth
reconstruction. In Proceedings of the XXII Conference on Groundwater in Siberia and Far East, Yakutsk,
Russia, 22–26, June, 2018; pp. 291–297. (In Russian)
65. Kharaka, Y.K; Mariner, R.H. Chemical Geothermometers and Their Application to Formation Waters from
Sedimentary Basins. In Thermal History of Sedimentary Basins. Methods and Case Histories; Naeser, N.D.,
McCulloh, T.H., Eds.; Springer: New York, NY, USA, 1989; pp. 99–117.
66. Naumenko, A.D.; Naumenko, M.A. Main patterns of high-potential reservoirs in the northeastern Black
Sea. Geologiya i Poleznye Iskopaemye Mirovogo Okeana 2008, 4, 49–58. (In Russian)
67. Smyslov, A.A. Geothermal Map: Map of the Crustal Heat Flow Regime in the USSR Territory. Scale 1:10000000.
Ministry of Geology: Moscow, USSR, 1977. (In Russian)
68. Kikvadze, O.E.; Lavrushin, V.Yu.; Pokrovskii, B.G.; Polyak, B.G. Isotope and chemical composition of
gases from mud volcanoes in the Taman Peninsula and problem of their genesis. Lithol. Miner. Resour.
2014, 49, 491–504, doi:10.1134/S0024490214060066.
69. Shatsky, V.; Sitnikova, E.; Kozmenko, O.; Palessky, S.; Nikolaeva, I.; Zayachkovsky, A. Behavior of
incompatible elements during ultrahigh-pressure metamorphism (by the example of rocks of the
Kokchetav massif). Russ. Geol. Geophys. 2006, 47, 482–496.
Minerals 2018, 8, 344 38 of 40

70. Saryg-ool, B.Yu.; Myagkaya, I.N.; Kirichenko, I.S.; Gustaytis, M.A.; Shuvaeva, O.V.; Zhmodik, S.M.;
Lazareva, E.V. Redistribution of elements between wastes and organic-bearing material in the dispersion
train of gold-bearing sulfide tailings: Part I. Geochemistry and mineralogy. Sci. Total Environ. 2017,
581–582, 460–471, doi:10.1016/j.scitotenv.2016.12.154.
71. Lavrent’ev, Y.G.; Korolyuk, V.N.; Usova, L.V.; Nigmatulina, E.N. Electron probe microanalysis of
rock-forming minerals with a JXA-8100 electron probe microanalyzer. Russ. Geol. Geophys. 2015, 56,
1428–1436, doi:10.1016/j.rgg.2015.09.005.
72. Beckhoff, B.; Kanngießer, B.; Langhoff, N.; Wedell, R.; Wolff, H. Handbook of Practical X-ray Fluorescence
Analysis; Springer: Berlin/Heidelberg, Germany, 2006.
73. Hubert, F.; Caner, L.; Meuner, A.; Ferrage, E. Unraveling complex <2 µm clay mineralogy from soils using
X-ray diffraction profile modeling on particle-size sub-fractions: Implications for soil pedogenesis and
reactivity. Am. Mineral. 2012, 97, 384–398, doi:10.2138/am.2012.3900.
74. Guggenheim, S.; Bain, D.C.; Bergaya, F.; Brigatti, M.F.; Drits, V.A.; Eberl, D.D.; Formoso, M.L.L; Galán, E.;
Merriman, R.J.; Peacor, D.R.; Stanjek, H.; et al. Report of the Association Internationale Pour L’Étude Des
Argiles (AIPEA) Nomenclature Committee for 2001: Order, Disorder and Crystallinity in Phyllosilicates
and the use of the “Crystallinity Index”. Clay Miner. 2002, 37, 389–393, doi:10.1180/0009855023720043.
75. Taylor, S.M.; McLennan, S.M. The Continental Crust: Its Composition and Evolution; Blackwell Science:
Oxford, UK, 1985.
76. Rudnick, R.L.; Gao, S. The composition of the continental crust Treatise on Geochemistry—The Crust;
Rudnick, R.L., Holland, H.D., Turekian, K.K., Eds.; Elsevier: Oxford, UK, 2003; pp. 1–64.
77. Romanek, C.S.; Jiménez-López, C.; Navarro, A.R.; Sánchez-Román, M.; Sahai, N.; Coleman, M. Inorganic
synthesis of Fe-Ca-Mg carbonates at low temperature. Geochim. Cosmochim. Acta 2009, 73, 5361–5376,
doi:10.1016/j.gca.2009.05.065.
78. Anovitz, L.M.; Essen, E.J. Phase equilibrium in the system CaCO3-MgCO3-FeCO3. J. Petrol. 1987, 28,
389–414, doi:10.1093/petrology/28.2.389.
79. Bau, M.; Dulski, P. Distribution of yttrium and rare earth elements in the Penge and Kuruman
iron-formations, Transvaal Supergroup, South Africa. Precambrian Res. 1996, 79, 37–55,
doi:10.1016/0301-9268(95)00087-9.
80. Bolhar, R.; Kamber, B.S.; Moorbath, S.; Fedo, C.M.; Whitehouse, M.J. Characterisation of early Archaean
chemical sediments by trace element signatures. Earth Planet. Sci. Lett. 2004, 222, 43–60,
doi:10.1016/j.epsl.2004.02.016.
81. Large, R.R.; Halpin, J.A.; Danyushevsky, L.V.; Maslennikov, V.V.; Bull, S.W.; Long, J.A.; Gregory, D.D.;
Lounejeva, E.; Lyons, T.W.; Sack, P.J.; et al. Trace element content of sedimentary pyrite as a new proxy for
deep-time ocean–atmosphere evolution. Earth Planet. Sci. Lett. 2014, 389, 209–220,
doi:10.1016/j.epsl.2013.12.020.
82. Cabral, A.R.; Radtke, M.; Munnik, F.; Lehmann, B.; Reinholz, U.; Riesemeier, H.; Tupinambá, M.;
Kwitko-Ribeiro, R. Iodine in alluvial platinum–palladium nuggets: Evidence for biogenic precious-metal
fixation. Chem. Geol. 2011, 281, 125–132, doi:10.1016/j.chemgeo.2010.12.003.
83. Meisel, T.; Horan, M.F. Analytical methods for the highly siderophile elements. Rev. Mineral. Geochem.
2016, 81, 89–105, doi:10.2138/rmg.2016.81.02.
84. Hagvall, K.; Persson, P.; Karlsson, T. Spectroscopic characterization of the coordination chemistry and
hydrolysis of gallium(III) in the presence of aquatic organic matter. Geochim. Cosmochim. Acta 2014, 146,
76–89, doi:10.1016/j.gca.2014.10.006.
85. Rice, C.M.; Atkin, D.; Bowels, J.F.W.; Criddle, A.J. Nukundamite, a new mineral, and idaite. Mineral. Mag.
1979, 43, 193–200, doi:10.1180/minmag.1979.043.326.01.
86. Hatert, F. Transformation sequences of copper sulfides at Vielsalm, Stavelot Massif, Belgium. Can. Mineral.
2005, 43, 623–635, doi:10.2113/gscanmin.43.2.623.
87. Hámor-Vido, M.; Viczián, I. Vitrinite reflectance and smectite content of Mixed-layer illite/smectites in
Neogene Sequences of the Pannonian Basin, Hungary. Acta Geol. Hung. 1993, 36/2, 197–209.
88. Stefanov, Y. Illite/smectite diagenesis and thermal evolution of Lower Cretaceous-Paleogene successions
in the Dolna Kamchiya Depression, Eastern Bulgaria. Geol. Balc. 2018, 47, 3–21.
89. Huang, W.-L.; Bassett, W.A.; Wu, T.-C. Dehydration and hydration of montmorillonite at elevated
temperatures and pressures monitored using synchrotron radiation. Am. Mineral. 1994, 79, 683–691.
Minerals 2018, 8, 344 39 of 40

90. Huggett, J. Low-temperature illitization of smectite in the late Eocene and early Oligocene of the Isle of
Wight (Hampshire basin), UK. Am. Mineral. 2005, 90, 1192–1202, doi:10.2138/am.2005.1674.
91. Hall, P.L.; Astill, D.M.; McConnell, J.D.C. Thermodynamic and structural aspects of the dehydration of
smectites in sedimentary rocks. Clay Miner. 1986, 21, 633–648, doi:10.1180/claymin.1986.021.4.13.
92. Morse, J.W.; Luther, G.W. Chemical influences on trace metal-sulfide interactions in anoxic sediments.
Geochim. Cosmochim. Acta 1999, 63, 3373–3378, doi:10.1016/S0016-7037(99)00258-6.
93. Rue, E.L.; Smith, G.J.; Cutter, G.A.; Bruland, K.W. The response of trace element redox couples to suboxic
conditions in the water column. Deep-Sea Res. 1997, 44, 113–134, doi:10.1016/S0967-0637(96)00088-X.
94. Cutter, G.A.; Moffett, J.G.; Nielsdóttir, M.C.; Sanial, V. Multiple oxidation state trace elements in suboxic
waters off Peru: In situ redox processes and advective/diffusive horizontal transport. Mar. Chem. 2018, 201,
77–89, doi:10.1016/j.marchem.2018.01.003.
95. Mucci, A. Manganese uptake during calcite precipitation from seawater: Conditions leading to formation
of pseudokutnahorite. Geochim. Cosmochim. Acta 1988, 52, 1859–1868, doi:10.1016/0016-7037(88)90009-9.
96. Böttcher, M.E. Manganese (II) partitioning during experimental precipitation of rhodochrosite-calcite solid
solutions from aqueous solutions. Mar. Chem. 1998, 62, 287–297, doi:10.1016/S0304-4203(98)00039-5.
97. Millero, F.J.; Feistel, R.; Wright, D.G.; McDougall, T.J. The composition of Standard Seawater and the
definition of the Reference-Composition Salinity Scale. Deep-Sea Res. 2008, 55, 50–72,
doi:10.1016/j.dsr.2007.10.001.
98. Zachara, J.M.; Cowan, C.E.; Resch, C.T. Sorption of divalent metals on calcite. Geochim. Cosmochim. Acta
1991, 55, 1549–1562, doi:10.1016/0016-7037(91)90127-Q.
99. Alwan, K.A.; Williams, P.A. Mineral formation fromaqueous solution. Part I. The deposition of
hydrozincite, Zn5(OH)6(CO3)2, from natural waters. Transit. Met. Chem. 1979, 4, 128–132,
doi:10.1007/BF00618840.
100. Abanda, P.A.; Hannigan, R. Effect of diagenesis on trace element partitioning in shales. Chem. Geol. 2006,
230, 42–59, doi:10.1016/j.chemgeo.2005.11.011.
101. Rajan, S.; Mackenzie, F.T.; Glenn, C.R. A thermodynamic model for water column precipitation of siderite
in the Plio-Pleistocene Black Sea. Am. J. Sci. 1996, 296, 506–548, doi:10.2475/ajs.296.5.506.
102. Campbell, K.A. Hydrocarbon seep and hydrothermal vent paleoenvironments and paleontology: Past
developments and future research directions. Palaeogeogr. Palaeocl. 2006. 232, 362–407,
doi:10.1016/j.palaeo.2005.06.018.
103. Roberts, H.H.; Feng, D.; Joye, S.B. Cold-seep carbonates of the middle and lower continental slope,
northern Gulf of Mexico. Deep-Sea Res. Part II 2010, 57, 2040–2054, doi:10.1016/j.dsr2.2010.09.003.
104. Matsumoto, R.; Ryu, B.J.; Lee, S.R.; Lin, S.; Wu, S.; Sain, K.; Pecher, I.; Riedel, M. Occurrence and
exploration of gas hydrate in the marginal seas and continental margin of the Asia and Oceania region.
Mar. Pet. Geol. 2011, 28, 1751–1767, doi:10.1016/j.marpetgeo.2011.09.009.
105. Bruland, K.W.; Lohan, M.C. Controls of trace metals in seawater. In Treatise on Geochemistry; Elsevier:
Amsterdam, The Netherlands, 2003; Volume 6, pp. 23–47.
106. Tribovillard, N.; Algeo, T.J.; Lyons, T.; Riboulleau, A. Trace metals as paleoredox and paleoproductivity
proxies: An update. Chem. Geol. 2006, 232, 12–32, doi:10.1016/j.chemgeo.2015.02.026.
107. Huerta-Diaz, M.A.; Morse, J.W. Pyritization of trace metals in anoxic marine sediments. Geochim.
Cosmochim. Acta 1992, 56, 2681–2702, doi:10.1016/0016-7037(92)90353-K.
108. Janssen, D.J.; Conway, T.M.; John, S.G.; Christian, J.R.; Kramer, D.I.; Pedersen, T.F.; Cullen, J.T.
Undocumented water column sink for cadmium in open ocean oxygen-deficient zones. Proc. Natl. Acad.
Sci. USA 2014, 111, 6888–6893, doi:10.1073/pnas.1402388111.
109. Awid-Pascual, R.; Kamenetsky, V.S.; Goemann, K.; Allen, N.; Noble, T.; Lottermoser, B.G.; Rodemann, T.
The evolution of authigenic Zn–Pb-Fe-bearing phases in the Grieves Siding peat, western Tasmania.
Contrib. Mineral. Petrol. 2015, 170, 17, doi:10.1007/s00410-015-1167-y.
110. Lane, T.W.; Morel, F.M. A biological function for cadmium in marine diatoms. Proc. Natl. Acad. Sci. USA.
2000, 97, 4627–4631, doi:10.1073/pnas.090091397.
111. Morel, F.M.M. The oceanic cadmium cycle: Biological mistake or utilization? Proc. Natl. Acad. Sci. USA
2013, 110, E1877, doi:10.1073/pnas.1304746110.
Minerals 2018, 8, 344 40 of 40

112. Mederer, J.; Moritz, R.; Zohrabyan, S.; Vardanyan, A.; Melkonyan, R.; Ulianov, A. Base and precious metal
mineralization in Middle Jurassic rocks of the Lesser Caucasus: A review of geology and metallogeny and
new data from the Kapan, Alaverdi and Mehmana districts. Ore Geol. Rev. 2014, 58, 185–207,
doi:10.1016/j.oregeorev.2013.10.007.
113. Varentsov, I.M. Manganese Ores of SuperGene Zone: Geochemistry of Formation; Springer: Berlin, Germany,
1996.
114. Berner, Z.A.; Puchelt, H.; Nöltner, T.; Kramar, U. Pyrite geochemistry in the Toarcian Posidonia Shale of
southwest Germany: Evidence for contrasting trace-element patterns of diagenetic and syngenetic pyrites.
Sedimentology 2013, 60, 548–573, doi:10.1111/j.1365-3091.2012.01350.x.
115. Large, R.R.; Bull, S.W.; Maslennikov, V.V. A carbonaceous sedimentary source-rock model for carlin-type
and orogenic gold deposits. Econ. Geol. 2011, 106, 331–358, doi:10.2113/econgeo.106.3.331.
116. Berner, R.A. A new geochemical classification of sedimentary environments. J. Sediment. Res. 1981, 51,
359–365, doi:10.1306/212F7C7F-2B24-11D7-8648000102C1865D.

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